-------
Dry particulate removal from gases can be accomplished by several
methods (shown in Figure 5.1-1 and reviewed in Table 5.1-1). The baghouse
(fabric filter) collector operates by passing the dust-laden gas through a
fabric network that acts as a dust filter. Its removal efficiency is over
99% and operating, costs are low compared to other approaches. ;The electro-
static precipitator, which also has a high removal efficiency, affords
separation of dust by passing the dust-laden gas through an electrostatic
field. The dust particles become charged and migrate to collector plates.
Another technique is the cyclone separator which operates on the;principle of
centrifugal force. The dust-laden gas enters the chamber tangentially. The
dust particles have a higher inertia than the gas, so they travel to the wall
of the cylindrical or conical chamber and then into a receptacle. The
removal efficiency for cyclones varies from 50 to 90 percent. In the
impingement process, the dust-laden gas impinges on a body which:collects the
particles as the gas deflects around the body. The removal efficiency is 0
to 80 percent. The simplest mechanical separator is the settling chamber.
The dust just settles to the bottom of the tank due to its heavier mass,
resulting in a removal efficiency from 0 to 50 percent.
Wet collectors require mixing the dust-laden gas with; an aqueous
solution that captures and removes the dust particles from the gas stream.
Examples of such, equipment are shown in Figure 5.1-1 and described in
Table 5.1-1. In the venturi scrubber, the gas and liquid pass through a
throat at a high velocity, promoting collisions between the dust and liquid
droplets. These units require a high pressure drop (~50 in. H20) and have
removal efficiencies of greater than 90 percent. Another wet scrubber, the
impingement-pi ate type, consists of a perforated tray with an: impingement
baffle located above each perforation. A liquid level maintained over the
trays collects the dust as the gas passes through it. These units are
similar to the venturi scrubber and have about the same removal efficiencies;
however, the process requires a larger pressure drop across the plates.
Another type of wet scrubber is the spray tower; it utilizes cquntercurrent
spraying of liquid droplets to remove the dust particles by impaction at an
efficiency of 50 to 80 percent. The operation of the wet cyclone scrubber is
similar to that of the dry cyclone except liquid is introduced jinto the gas
stream, removing the dust by inertia! impaction. The removal efficiency of
the wet cyclone is 50 to 75 percent. The wet electrostatic precipitator
operates under the same principle and at about the same efficiency as the dry
precipitator.
Control of fugitive sources. Wet dust suppression can be 'used for the
containment of fugitive dust. This process consists of spraying the dust
source with water or a foam suppressant which traps the dust and prevents it.
from becoming airborne. The foam sprays are relatively inexpensive, consume
less water than pure water sprays, and are very effective. In a foam spray
system, foam is produced by pumping a mixture of water and a surfactant
through an air atomizing nozzle which produces small bubbles of approximately
100 to 200 microns. These wet bubbles are broken by contact with dust,
coating the particle. The foam is only effective when applied directly to
the source, such as on a conveyor, or to a falling stream of material, such
as at a conveyor transfer point. Once the wetted dust agglomerates with
other particles, it no longer becomes airborne at subsequent transfer points.
172
-------
The suppression (or removal) efficiency is 95 to 99% in terms - of: the material
contacted. . . •'
Paving the heavily traveled roads with a hard surface and providing
vegetative covers for the disturbed areas are additional technologies for
reducing fugitive dust emissions. These technologies are described in
Section 5.3.
Particulate Control Technologies Analyzed— -
The TOSCO II plant- has two major areas where particulate matter is
produced and must be controlled: (1) raw shale mining, crushing, conveying,
and storage, and (2) shale pyrolysis.
Dry dust is generated at point sources, such as the primary and secon-
dary crushers, and at the enclosed fine ore storage area. For these point
sources, baghouses were examined for particulate removal due to their high
removal efficiency, relatively low operating costs, and the dry hature of the
particulate.
The flow rates and particulate removal efficiencies reported by Colony
(Colony Development Operation, 1977) were used as the design basis for
estimating the size and cost of the baghouses. Depending upon: the type of
dust, particle size distribution, and grain loading, the baghouses were
designed with an air-to-cloth rati-o of 5.9-6.7 to I (ACFM to sq. ft. of
cloth), using Dacron HCE filter bags. The baghouses are equipped with
adjustable pulse durations and cycle times for compressed air discharge
through rotary airlock valves. When in multiples, the baghouses are mani-
folded to a common self-cleaning inlet, allowing part of any baghouse system
to be shut down for repairs without taking the entire baghouse out of
service.
In the shale pyrolysis process, hot, sticky shale dust is generated at
three points: the raw shale preheater, the ball circulation system, and the
processed shale wetter. For these point sources, venturi wet scrubbers were
evaluated due to their high particulate removal efficiency and the wet,
sticky properties of the dust. Again, the information reported by Colony was
used as the basis for the design and cost estimates. The high energy
scrubbers used for the shale preheater require a larger pressure drop than
conventional scrubbers. . . •
Fugitive dust is generated from mining and blasting, raw and processed
shale conveying, conveyor transfer points, baghouse dust discharge points to
conveyor systems, truck loading and unloading, and disposal operations.
These fugitive sources of particulates are controlled by water arid foam spray
suppression. This system is inexpensive and offers low water consumption arid
high removal efficiency.
In addition to the major particulate sources mentioned above, there are
several minor point sources, such as the furnace and boiler stacks, for which
no controls are applied. .
173
-------
Table 5.1-2 lists the design parameters for each of the baghouses and
venturi wet scrubbers examined. The capital, operating, and annual costs for
the particulate control equipment are presented in Table 5.1-3.
Figures 5.1-2 and 5.1-3 present the cost curves for the baghouses and venturi
wet scrubbers, respectively.
Total Particulate Emissions—
The controlled particulates from the point as well as fugitive sources
are summarized in Table 5.1-4, along with the type of control technology
examined for each source. The uncontrolled emissions are also included in
the table to give total particulate emissions from the commercial operation.
Estimates for these emissions were taken from Colony's PSD permit application
(Colony Development Operation, 1977).
5.1.,2 Sulfur Control
Processing of sulfur-containing fossil fuels will result in emissions of
sulfur compounds, such as H2S, COS, CS2, RSH, etc., or their combustion
product, S02. Federal and State standards limit sulfur emissions because of
their potentially hazardous effects on human health and the environment.
Inventory of Control Technologies—
Two general categories of technologies are available for the control of
sulfur emissions: (1) removal of sulfur compounds from flue, gases after
combustion (sulfur dioxide removal, or flue gas desulfurtzation) and
(2) removal of sulfur compounds from gases prior to combustion (hydrogen
sulfide removal). Several technologies in both categories offer recovery of
sulfur in a useful form, while others chemically fix the sulfur compounds on
a reagent which then requires disposal.
Sulfur dioxide control (flue gas desulfurization). Removal of sulfur
compounds from flue gases—that is, flue gas desulfurization (FGD)--is based
on the physical and chemical properties of S02 because fuel-based sulfur is
usually converted to S02 upon combustion. Flue gas desulfurization can be
divided into two categories:
* Wet scrubbing i :
• Dry scrubbing.
!
Wet scrubbing utilizes a solution or a slurry to absorb the S02. Dry
scrubbing uses either a dry reagent bed or an atomized solution of an aqueous
reagent at a high temperature to remove the S02. Both categories can be
divided into regenerable and nonregenerable processes. The different types
of S02 removal processes are shown in Figure 5.1-4, and Table 5.1-5 gives a
brief description of each process.
Wet scrubbing—The regenerable wet scrubbing processes generally employ
a clean alkaline solution to absorb S02 in a scrubber. The resulting spent
solution is treated with an insoluble alkali makeup which precipitates the
174
-------
in
ce
UJ
t
3S
QC
^C
&
3E
UJ
O
|
£
32
CL
— ^
o*
Ul
.rij)
§
^—i
o
UJ
1—
3
3
1*4
1
04 '
t
H
tfj
UJ
_J
rf
t-
tO C *-.
r- r- O i-
a 3 •«- j=
•p u in "N,
O.i- in ja
£- 's C1
10 uu
0,
<— u
IO C
§ 5$
. OS 'C
K-
UJ
-o
ffl /"^
O S.
-I J=
•p .a
in r-r
3 v-»
a
a>
P ^-v
10 .C s
ce u u.
(O U
3 LLJ ,
E
•r—
£-
CL
in
3
O
en
10
ca
CO
IS O
in in
en en
i^* r**
tp tf\
CO UD
rH rH
O O
o o
0 O
s? ?
rH rH
r— i-
01 Ol
3 r— C
I— i-
£ 4)
•i- »- tS
IS OT Ol
r- .C 01
u id u.
ai s.
ce r—
ai at
in in
3 3
O O
J= -C
0) 0)
10 10
ca ca
<* in
en
CS1
CO
OT
OT
f^.
10
en
o
rH
O
O
0
CM
^
S.
in
3
S.
O
Ol
c
u.
01
in
3
O
.C
a) .
to
ca
us
IN
^i
oi
en
O
cs
0
rH
O
O
0
IO
rH
0)
£
o
a>
i.
o
Ol
c
u.
01
in
3
O
cn
10
ca
•*•
0
rH
CO
a»
cn ,.
o
o
0
in
o
•«•
o
o
CM
rH
CM
10
•P
10
01
j.
a.
II
i/) in
f^
i.
01
J3
3
i. >->
0 >i
l/> O)
•P
-P -C
01
s
00
r*I
CO
eft
cn
a
o
0
cn
CO
rH
O
O
CO
5
10
c
0
IO
3
U
S- S
C w?
to
ca
i.
ai
ja
3
S.
y
0)
. 3
s.
3
C
O)
en
rH
CO
CO
CO
1
cn
cr>
O
C3
CO
CO
CO
O
O
5
IO
01
-C 01
cn N
•I*
•a s.
01 3
in *»
in in
01 •!-
a.
j_
at
3
i.'
J»!
>, c: u
01 'r0 O
> O -P
c a. ui
o
u
in
10
i.
a.
e
10
o
u.
TJJ
C
to
s.
01
-p
*JE
cn
CO
rH
CO
IS
•U
o.
0)
•w
Iri
O
(A
S
u
01
-p
c1
•r-
U
C
01
•r-
U
H—
*+•
ai
ai
•a
0)
^_>
o
•P
c
o
u
to
si
ai
+j
IB
s
01
j= -a
-P 01
•P
. '— O
o c
"T
el t ^
in ai -P
"4^- o> ai
>) Ol
Is" iC
•r- 10 P»o
os. cn
•r? 0) rH
4— "O
Hi -r- -
at in e
, C 0
r— O *r-
10 U -P
> IO
§0) t-
J3 01
ai a.
s- "a . o
10 3 J->
0 =
cn 3 ai
C €
•r- in a.
in ai O
3 +J r-
10 ai
Or— >
UJ 3 Ol
3 u a
1/1 V-
1 •P >>
>1 S- =
a. r—
TJ 0
01 ai o
•P C
18 S.
SO
•r- J3 0)
•PS.
-------
§
5
o
i
§
o
tu
^c
sj
o
1—
<
CU
u.
o
t/>
0
u
•
1
«H
tfj
1
- *
10 tn
C 't— O
coo
•* tj 0
<"* £Z ^%^
10 O
•U CJ *J
O in
1— O
U
i— • in
10 Oi-
3 e o
C-i- 0
c -u o
< 0 <«•
£• ^^
"ie O.-P
-p o tn
0 O
1- 0
' ^ ^*>
to tn
is
fo O
Tg"^
X in
•i- O
u. o
2
to /—s
*11
o LU •
O U
O tn
CU
a
11
•P 3
I/) Z
CM
rH
^»
5
o
o
in
rH
•p
c
O
a.
1
to
i
. S.
t-
"a
o
a.
CU
3
O
a>
10
CO
CM
!-• CO
H rH
CM tfl
** "
o m
to rH
O O
O O
iH 0
CM CO
{Q ^t"
rH rH
1 "3
S §
S- 2
0 H-
| 1
Z CU
a. ce.
cu o>
10 10
CO CO
CO «•
S
T-H
CM
l-t
oo
CO
o
o
0
•a-
<*•
iH
C .
00
CU
t.
10
CO
tn
0
to
rH
cn
§
rH
CM
0
O
o
CM
,3.
S.
CU
&
in
3
S_
CU
c
u_
Ol
3
O
f
CD
U)
in
00
1*^.
OJ
S
CO
o
to
CO
r_(
IO
1
HI
!-
O
1
ul
CM
CM
in
rH
O
O
CM
O
o
o
CM
rH
CM
to
S
u)
>.
V)
Preheat
31 .
15
.e
3
10
O£
O
•P cu
CU i. C
S CU Ctl
a
3 Stf '^
•P U J=
C VI s»«"'
>
S
CO
CO
CM
CM
O
cr>
I-H
CM
O
O
ro
' *
IO
g
•2
U)
c
_o
^j
10
3
a
u
IB
CO
CU i-
*^g ^
r\
•i- .a
&. 2
3 '-
•P U
C 00
CU
S
in
**"
in
CM
0
CO
CO
i-T
o
o
"3"
•3-
to
i.
11
M
S.
3
tn
i.
«>
1
•o
0)
tn
01
11
u
£
a.
^
11 S.
• (-1
3 S-
•P U
C I/I
D
O
CM
CM 0
CO 00
CT> rH
§5-
S- U
S. U?
Is
> a.
§°
o
f.
o
u. .
•o
c tn
j^ j^
"«•
3*
•P O
!-
*• a.
o
c
c _o
10 p
3 C3
t 1=
o •»-
u
c
c o
o
•o
U)
-------
% 1S03 9NllVH3dO 1W1NNV 103MIQ
o
CVJ
LU
to
£O
O
03
_
o
o
LU
_1
=1
1—I
£
Q-
U_
O
f—
O
O
CM
O
o
rO
O
in
% 'iSOO "IVlldVO Q3XU
o
a,
o
-------
.01 2 'ISOD 9NUViJ3dO 1VHNNV 133810
8
o
S3
co
o:
03
DO
— £E
£
oe
% ^g
Q. CD Q-
I I
-------
TABLE 5,1-4. TOTAL PARTICULATE EMISSIONS FROM THE PLANT
Stream
Number Emission Source
2
3
4
5
6
7
10
18
19
20
91
.104
118
119
125
138
179
Portal Transfer Point
Primary Crusher
Reclaim Tunnel
Transfer Tower Feed Bin
Fine Crusher
Fine Ore Storage
Mine Vent
Raw Shale Preheat System
Ball Circulation System
Processed Shale
Moisturizer
Hydrogen Furnace
Coker Feed Heater
Gas Oil Heater
Gas Oil Reboiler
Naphtha Heater
Diesel Equipment
Utility Boiler
8, 139 Conveyor Transfer Points,
Open Stockpiles, etc.
TOTAL
Parti cul ate
Control Description Emissions (lb/hr)
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
. —
Venturi Wet Scrubber
(high energy) .
Venturi Wet Scrubber
Venturi Wet Scrubber
—
— ,
-- ' '
-- . . •
: — '
Catalytic Converters
—
Water and Foam Sprays
,0.5
7.2
5.6
5.0
32.9
4.2
•• 25.0
81.0
37.8
38.3
; 11.4
1.1 •
0.4
' 1-6
0.2
: 19.0*
2.9
29.8*
303.8
Source: Colony Development Operation, 1977, except those quantities noted
with an asterisk (*) were estimated by SWEC.
179
-------
REGENERABLE
PROCESSES
NON REGENERABLE
PROCESSES
REGENERABLE
PROCESSES
• WELLMAN-LORD
• MAGNESIUM OXIDE
- ABSORPTION/STEAM
STRIPPING RESOX SYSTEM
• LIMESTONE
•LIME
-DOUBLE ALKALI
• SODIUM CARBONATE
-OOWA ALUMINUM SULFATE
- OIL SHALEf PROCESSED
SHALE, NAHCOLITE)
-CHIYODA THOROUGHBRED 12!
•AQUEOUS CARBONATE
NONREGENERABLE
PROCESSES
— LIME
SODIUM CARBONATE
L—OIL SHAL£( PROCESSED
SHALE, NAHCOLITE)
SOURCE: SWEC
FIGURE 5.1-4 SULFUR DIOXIDE CONTROL TECHNOLOGIES
180
-------
V)
UJ
3
o
u
UJ
H- '
— J
H—
O
UJ
O
O,
o
os
3
U.
l/>
U.
o
V)
LU
ce
S
u.
UJ
tf»
ifi
LU
' _ J
s
U)
8,
id
m
TJ
(0
Ul
O
(A
Oi
1
1 (0
TJ
C
S u>
Q. 3
O •(->
Ol 4J
> VJ
(U
o
4C
ortnance
£.
°-
a.
u
c:
a.
c
4- t.
o
r— Q.
am
4- o
*3 3
ai o
or u>
N O
o •»-»
V)
TJ
•a C —
U (d 3
C (J ui .
0 TJ
u -C ai -i-
U r- U
fo •»- .a m
jc id
ui 3 t— u
a>- tO T-
U S w S-
3 (0 3
TI at ai **-
O S- -^ r-
S- -P rO 3
Q_ Ul S (A
TI
r— I C
O 0)
O) O •
es 3
s c
0) +J
o s.
co to c
+•> U) C
3 *J C (d
O "- O Q.
.a c •(- as
^ 3 +•* ^
OJ
W- O
0} (0
<— s.
3 C
o ai
J= O >
u v> o
3 ift
TJ UJ-
at nj o
c -c
SOU
TT 3
Ul O -C
Ul *•> O
n w
•;iE||
3 ui 0) "O O
"£•£ OJ +J
O «*- r- 3
•J3 "3 "° 'o
U> U>
i,
O
-J
c
ra
e
"«
3:
1
o
v>
TJ
C
m
«*-
o
c
>
,£
2
flJ
t_
it)
'*
•a
enerate
a*
Of
S--
U)
c
at
01
0)
aj "O
J= 'C
V ro
S- S-
O 0)
3 V
VI
ui O) i-
O) S Q)
*3 o'ju
as E u
"*-
o
01
i.
S 3
(O -f*^
1- rd
Ul "3
C
94 (Q
C O U
Ul 01 O
O) 1— "I"
U J3 t-
3 (TJ 3
TJ *J *t-
2*3*3
O_ ui ui
C
o 3:
nj O> C O
s- 3
S rd C O
O) -C -I— j3
UJ -O
at •*-> 01 -C
ai c -M u
f r— OJ OJ
0)
r— C
O) fO
— £.
3 C
O Q)
U
-C O >
+j o e
Sc«g:
U V) O
3 in
T3 U»
o) m o
OS Cl-H
E
1S"S
.r- S. -»- 0)
UJ .(J S. 4-1
c 's-
CTTJ vt 0>
rtj 3 S- OJ
i- :.
•"= < ,2
*3 i °* **
« ^"c "S
o s- o c
to 3 Q.-I-;
S- 01 JS (J
O.TJ -(-»
UJ *»~ TT
^2 X *- C
§
U) rd
at a>
C TI
O) -^
-f-
i— -a 4J
•i- U
C 3
C4 (d C V»
J
C Ul
(O
IS
X *0
O •(->
3
•r- TI
U>
Ol CO *->
a> a> o1
ra u to
OJ 'O O
J= S- r-(
***
TI
0)
nj
Ul O)
1%
a; ui
TJ
C 01
O) C
Ol -p-
J3 ^
00
(d
U)
. rd ui
a: m
.2SS
&SI -
U U) i—
O >» O)
IA Ul
C -Q
r— O_r—
to. id
•r ui
Ul *J Ul
u* at .
Ul (O TJ H— -
O) O> O *—
Ul *J S- 3
O UJ Q. UJ
OU ui C
a> 4-J s_ a. c 01 c
td m o c a; .
^ O. C -r- "- O)
01 o -*-> .n \n
ui ui •<- ra e
S 4-» £- O w»
O) C td *J O rd
-fcJ -r» i. Ul ^ TJ
ui -tJ c ai ai
>»TJ UJ O .C S ui
ui a> c s 4J a; o
Ol UJ S TJ S- Ul O
.c 01 a> o >» s-
Ol
3
f— C
*- O
•*•> -M
o> rd
.— S. a
3 a '
a 01
u
at c •
5S|
ui 04 Q.
OJ O
U tft-O
TJ U)
O» rtJ O
Q£ O)4J
O C
TJ . - 0> •»•> J= U i-
. -f- O Ot OI O> tJ UJ
C Ol U V) O)J= -tJ Ul O» O tO
O -^^ O) (O *i- JZ *J (/>
.)- • aj t- e s- (A . uj
4J -fJ 0) J= m 4J -N 3 S S- U
'oa)cu)'r"u»utou«»^ £
irt 03 O ,Q !± C OJ ^= >, 3
OJ J3 S- O ** O -C +J UJ UJ O
u>S-.!-0-£OUl--£X(_ 2
O
nj:£'-5.12oi*'""otirda>a; vi
= 3oo^>»>-*Joi^:'—
s
C UJ
•f— n) — J
a. E an
**s. o. at ^
O I- ui UJ
•*J V> tO UJ
a. C3
o 1 o a
ui Ol ui Z
J3 -W O) O
< tO Q£ Z
ai ai
* - S 5
>v Ol C rQ ra (0
+J C O t- C • t»,
.,_ ,r» ,r- d) .»» ui Q),
^-f-«fA> U)«*--M>1
••- ra o o -r- o u) o
_a o s- o . s. o u
ra ui S- O) O) U 0)
s_ o t- 01 uj s-
aiocjc s_ 3 >, c
O T3 C U S- C
7-3»
i. o s- u i— s- s-
(d O •*- 3 TI O> 3'
•W U) <^» Ol *r— JS <4— t
ui u o f— so. air-
3^t4_OIV) _J(_JZtO
s :
5 ^*r- '
c c: ro a) aj > c
•»- 01 c e -F- o o
+j > o -f- +j e *>
(O O •*- r— C Ol U>
s- i- -M a> s- 01
o) a. c oj 4J s
tTL 0> • -J3 O M»r"
O TJ > ••-* -U O.O •—
c c c • to i
TI nj O OI O C C
C US +J rd S. rd
*- Q.4J 3 rd TJ m
tOS"-0- ^-C0)>,
*> -r- 3- Ol 'i- rtj S- O
•f- VJ .S O) C
CL (A U) -f- U> Ol
CO UJ U) ui u> *Q *r~
u • ai 01 01 u
§ui O O t. O > "4-
o s- s- a> s- T- «*-i .
— 1 U Q. O. >Q.O)O[
:
C • C
O O
'"T +^ *"3 "Ji i
•r- !_ -r- S_
U Ol U O)
t- a. s- a.
ai o o> o •
S CJ ^ Ol
§~ c: TJ s c TJ ;
•— -r- O -f- -f-
c1^ T c*« *Z ,
(d C O JT o > '
+J U E -PUS1
a. a.
u> « a. u> « o> '
TJ tA TJ UJ >
-OS Ol+J OS 01*>
Ol C C
5 o >*- o <*-
ui O O
•i— OI r*- OJ •)— 0) *"• OI
r-£.4jQ. taui»a.
S- Ul S- Ul
j- TJ ro ••- J= TJ ra -F-
*J Ol Q.T3 -<-> Ol O.TJ
' 3 ^ ui TI *3 r2 ul TJ
94"° "~ S . w"0"" m .
0<>, r- O» *—
10 t?^: ^ -fc'8^
ui . 3 t. t- tA .Si-'V-
J3 >»r— 0> TJ -J2 >v— Ol TI
i. 4- VJ -*-> C S- S. VI J-» C
ui3OJ3»— U13OI3I—
£J *— JZ Q) ^«— £01
.C
o
ul r8 !
0) g
E . E
J ' ^
181
-------
u>
s,
03
S
«J
1
Ul
vantages
S
+->
c
03
13
O -P
r— 03
Ot 4->
> VI
o
1
Ji
*p*
at
a.
Ol
"a.
u
G
{_
a.
.=
£.
at
a.
O
O
'g'o
if C
•*•» US
G U
O t—
US' 01
03 Vt &
Ol •*•» «
t. fO O1T5 i— S-
O TJ 3 "O G (O 41
U5 «P- VI t. i— O
ui at ui at E w
3 «p- . > at ua ••- i.
itJ Ot <"• C 'P~ US 3 73 C
T3 J* O U» H- *— O O
O ro o -f C Ouic
re CL • at u>
U) /"^ C 4J X P-" Ul «™ •>••-
01 4*S O *P- Q) (ft G ^
£- o •*- a. -f «t- -IB s.
•P- CJ 4J ••- G S. rtl US 3
crto-aoi •*•» c «j »—
• Ct£ *•«•» fO CL*p" &' (J i— V)
O)
C
0) 'X
c ua
as at c C I- -
t, at o o u
0) C <*- >P- •?- Ul
a. o o 4-> u>
O 4J 3 O Ol
•o S u> "o oi *->
C E 3 ui
r- US G C
rtj Ol *J *r- -P- c
*•» us Jar- o
a, 3 3 u ui
(0 4) U2 S» Ut O
U-* U S.
. -r- - Ul U) t.
e — E at o
*~ 4J +J nj 3 CL
o o >»/— at c o
— i o ui y i- «j r—
c 1
O +J
r- 4J J. C
u at c c
s. a. 3 o
flj O •<"•
S G 0) 0
O •)— 5- 3
U US S-
Ot 4J Ul
C i- -O C VI
•r- C G 0 •
S 3 at o O
Ol.
3
<4— O
«» 1o
!ZS ^t
3 C
O Ot
US 0 I
Ul O4
S v> S
"O v»
Ol OS O
OS O>*>
in" e C *P-
•p- "O ui (J (— o
*J O (4 T3 at 13
*— t/> u: -u cu-w o)
O -O ^- (0 £. U>
« e -*» s. ot « a
«j t^ at us a. a.
G 4> > Q) 0) 01 •<•-
•;- |0 C *> S S -0
(O X U **~ ti G" ^ r—
^£ O i— O 01 C -—
>i *p» "^ *»- i— ~b 13
ous -uactJoatc
3; ffl^o'auji.fl
3 T» 3 •*•> "O -M
ui*p- **••!— 3 at 01 (0 113
41 T3 P— -OP- S*J3
Z> UJ Ul Ul Ul r— V "O 'P~
13
(O
0)
i .
0
P3
Ot
> Ul
-F- 01
U> C
C 3
at -c
5-2
ot a.
c
(Q .
IA (0
US OJ
Ul -4-3
"O 3
w 2
UI
i cost. A very
reliable proces
as 13
+* C
'- aj
CL
S- CL
0) O
u ""
Ul
S- -4-1
3 -p-
O C
U. 3
at
,2 c
<4- O
"at "^
jj _u3
3 C
O 01
US O
+•> U
U9 01
Ol O
U VI
3
0) at a-
+J 3
Ul fO •*-
^ at *3
US TJ 01
u
S3 .
3 <4-
4-> O
41 ^-*
O> 3 41
•a u ui
3 -P- O
i™ W CL
W> <4- Ul
fO T3 "O
O>
•a
•a
o
1
CL
O
U)
J -o .
+•» C P-
3 « i—
o -o *»-
S "«*"
w -a c
u= >»""
ft. Ul
OS Q
at -a. CL
S- Ul
4J Ul -p-
4!
i
s*
at
o
u
t
=
c
(13
JL
s.s
nj a
at -i—
T3 T3
§•1
at os
ae. r—
Ul *t-
U) F—
at m
u •*.
Em
a*
- U r—
..p-"ua
Ul 3
(O O
ua -o
Ul
U)
Ot as
US
•»•» e
Ul -P-
Ot Ul
s-s
^
^
u
O)
U (/>
•o rj
o>
Ul Ol
3 US
•*•»
z-
3
r- C
**".2
4-4 -t-1
ot Ot
3o
1
3 ua
< i
10
lt therefore, ha
[vantages. The
:S a clear scrub
^3 T3 (O
S fl Ul
0>
process
the sara
process
Q.
0
4J
« g
OJ 0
Q. *J
«Si
i5?2
N
oi "o ot
(0 X (0
Ul -P^ UJ
I'll
r— O —
05 ui 03
',
1
1
1
-
"£
m
U
Ul
Ul
Ol
|
t-
us
u
i
c
solutio
2
C
O
+J
3
"o
S
3
•o
1
(/>
4->
id corrosion in
oop.
I?
c •»-
o ua
•r- U3
Ul 3
0 '*-
'- U
O) ui
C CL
*^o u
u -o
«s
regenerate
sulfate anc
•o
a»
S
(Q
^J
^
tj
a
u)
u
'us
3
^
"O
c
03
.^
o
•o
Ul
O
CL
w«
'•5
I
u
*J >*->
. at Q
• c •<"
at o s- at
'«.**" f2
>» u o
3= 0) Ul G
Ul
and operating
, an abundant
rocessed shale
t the plant sit
s plentiful in
e Basin.
p- O CL CO -P- U
2 ™ <*- =
•f 01
CL ua -r- u
3 j't^'S2
3 ui o. rtJ US
_J v ui «J 3Z +J
c
0)
/^ Ul *
C 'I— W
O -C -tJ O
ui C "-
•p- *J Q.
CO u>
41 «J C
§31 °
4- CL (8 "O •
at e m m
•r— C
<4- O
4-> *->
O) (0
r- 1.
11
U
53 .
Ul M £
O) O CL
U */» CL
3
•a u» o
Ol aj in
OS OJ t
4-
O '*—
o> o
us at p- ot
Ul U r«J Ul
,+j •.— o
(0 ui -w CL
•r- O) •
3 '"" V> T3 r— •
ui . 3 s. as
ua >»^- 01 f—
S. S, Ul 4J
w» 3 Ot 3
Ol Ot 01
r— Ul *J
IO W *i"
US Ol <-<—
V7 U 0» O
0 i— U
P- S. nj j-
"f &. US (Q
182
-------
0) N
tri u> tn
01 "-
4-> C
§511
Jsiif
+J VI 0)
U|.
-P OJ •— O) *»
c
01
•P
*O
O
J
•5
T3
0)
(A
3
|
3
"o
IA
C
O
01
c
0)
ra
(A
(A
O)
U
2
o.
S
*
c
ro
01
>
V)
O
&.
O
X 3
>1 V)
t. c
> u
u ro
3 U
O" V
as
£
5
i
n?
c
>
5
.
c
OJ
Q. 3
>- ro
01 4->
s *"
s
(3
' g
o
• E.
01
Q.
OJ
[a.
u
c
t.
a.
Operating
0°
£1
C .(J
U>
£ Q.
"5 O)
X. O f—
O -P 0)
tn
TD OJ (A
cr -w 01
" £ >
C4i™» t-
O 3 0
CO tfl -P
u
j-i 3 s
0 *U
tf) f— O)
,n ro c
•PUS
(A W &
O) O
U CO O
.3 (A
"<3 (A
Ol .« o
tJ a»
CO). +J .C O)
O S» OV *J *t-fl
•r^ (O - C C.
•M t- S. jQ N -*•>
W 3 C 3^0 -0
S. +J OP/— 3 CO 0) C
•^ ro jC (A ^3 J2 —
<*- 01 *J 0) b.
-C a >,
•2 2 "c § •^H" Ja s^
•i— ro •*•> ro 3
t/) tA ro • *—
4— , U 0) t- -C IA
fS 0-2 .2 §)££'£
i-iH^
ro O1••» +rf (O ** S»
u oj -P 3 -f- tl nj o> 01 >» M
•^ u>roa>3;s->> OJOS^^IA
j= -P QJ >,<*- ro aj +J u ro •«- ,.— -w S "*- u ja s ^Q ro -PC
.W Ul O -Q S- 03 O) S T3
CT C S- +J U •— 0) CO S-
c >,-f- t- O
r- -r- *J ,r- .^. .»-, -O J. l^_ 3 r- ^1
.a t* u o oit.-aofO'— •
v>
CO
UJ
o
§
a.
-C3
z
03
ca
§
s
. OS
a
UJ
-j
ca
S
s
UJ
ce
<03 ra
•P H- T3 C
C 0)
01 in S. ro
r- (0 Cv
0) r—
f» S.-r-
01 (O OJ O
r- O f
Q (J Q) 01
(O -r- f—
*m i*^ ro
tn o •"—
IA 3 ra
MU ro ro
3 ^
O (-* ro
G. > . T3
01 C *TO *« O)
U 0) 3 U -P
2 .£» -^ *" S-
Q. > *J O)
Ol -i— O OJ
01 > -0 r- 4J
ȣ J= 5 "5.5
01 -S
3
*. O
aj co •
r- S.
3 C
O 01
O) C >
J= O E
+* 0 Q.
j_ „ "^
0^ O O
•O w> 1
« or*.
§w
tfl •»—
3 >, E
-P O) i- -2 cs
•r- 3 O.T3.O
3 O~ u> O VI
(Q VI
t> ° .5 i£ **
+•» O O> J3
o -P ro tl o
•f» IA !- 3
IA T3 U U -P
ro ai in ro
Ol M S C
cists
ro
01 01
3 C
O O
s-s
a* ra
•xo
0)
4->
01 *r-
OJ -P "O
•r- C 3 0
1/1 >l'*J
•f- S C S.
4J 01 -P
rtj O t. OJ .
s- o s. c 01
in ^^ u o 3
ro 4.
c -2i u so*
•F- U S. 3 3"O
a) ro o &. P o i—
•P +J -C U «A 3
U Ul f— OJ fl IA
O 01 Q_ -P •»•• O ^
f— 01 SO
_g s. "^ § "~ * -o
O S- -r- rO
T3 01 -P (A '0)
ra 3 -P *" jC "(5 4J
O -f- -P O ra
•C Ol->- 3 '« O
•Q m a, a. > 3 u
r
J
(A ,«A
T3 ( 01 0)
S'S-P i— O ^ «C -i-» 3
3 o» O Ol 01 J3 3 .f— -i- *t-
•i— c^:vi^u>i3Cf—
O 3 01 U C Ul
(A-r-CC> 01CW
so s- 3 o :cn ro ns
«£ 01 ^* S 30 ^-0 " §
o H- ro x: 0) , j= 01
4J O1-PS.014I Or—
S- -r- 4J > -. Ot J-» O>
C f 3 01 rO r— .c
O01C £&.Ot—-PO)
.^ -o 01 -— -P 01 > cu
l3»llll;i»I
!
183
-------
^
c
o
u ,
t
t-t
in
UJ
1
UJ
J
fa
TJ
UJ
Q
UJ
o»
c
nj
>
3
^
c
(1)
is
O *J
F— <0
0) +-»
> V)
0)
o
•K
0
M
I
o
&.
ioatuj
*»- (Q S- -Q 4->F— S- U) > -r-
• >» F— a> N re •(- iOa)3 G O-F-O F^UJ'X'S
3 .— »— .a >» C >(— -(-> U , WJ 0) VI
r— -4-> ^ a» »— 03 o at o
•<- u s- at ai > *u *m -c -F- c -MOW •<—
•F» Ot C OJ -F- 3 -t-» F— Q i- F-« .Q
S S J= S. O 3 3
>^ U ">~~ UJ 2 IQ f" O Ot *•* Ul 'r— y> 4-> O
ui a) ^ 'i~ o i- fQ c ui c S- mjsnirau
•r* F— > 3 O> 3 ^ EO)
U)>) «i s- c
•PC
O UJ (0 UJ >^
0) "O -O
Ul I— O) •»-)
•r* TJ rtl ot
>» o) at E
UJ F^ 0) J= -5 .
to ,4J c a» F— m
O1JZ S- ui
Ol u) Ot O)
O) *r- *F-> U) £1 U
3 «- (0 -M O
i — ui ^ O) i. .
O) T3 (O O ja
U 3 Ol Ul -O O) 3
c -+-> j^ ui at , s s-
t/j uj s *-* c to uj
UJ O) C .
4-> C i- ' • ' O) 0)
•£ -F- fO 0) 1 •—
C J3 C (0
3 C t/1 O U
O O) -<-> i- ui E ui
r— .»- ai -F- a> . to oi
(O-*Ji-CT3. ^T30J--
•r- (0 JS 3 C C - M • •
(JS-h—3O ui (O ••-
I- 0) «— -r- Ul U)
S O • C f— (J U O C
§V1 O -(-> 3 " O O
C . -F- C S- S- TJ •—
•F- ^. U) +J (Q
§ai at "O i. c a> uj s-
1. JZ T3 3 O ^ O» +J
(— nj^rtJOU f- *J w .
at a)
c
•*— o <*— o •
+J -tJ -P 4J
0) to ai (fl
3 c i ' 3 e >
o 41 a. o at 0
JC < 0) C CU
w m +j u o
Ul OJ 1 ui dr-4
at o o ai o i
u v> o u vi tn
as o -*J " • as o) •«-»
c
j=ai •*- ^•f-h-vs-t.
•M rtJ .G T3 -P • -p O O
*»-J— ui.» s- «4r— ^ atco-aui+JOQ.
•PS-OJOF— *j. +jo.a.a.n ^-5^
U!-J3VJOO'-v U-F-S-Sfl-OOJO
nj 3 ^3 uatc^ m -P m t. c ra at
4Jfr-30J i—VJ 4->3U(jai,^^F-it-+J
.?- f— a) s-' TJ a> -t-t , M- at a t- i- S- »OCU1«J N> UJTJflJTJ'O*^
uj "O t. wi rtj 3 +4 UI«F- u dim
. Hj. o» -O ^ O-F- (tIEu)>» UJ4JO
OllM (0-JSQ. O»O3flJS'F-(jl_.
•F->»*OO)'F- +J O i- 3 0*-*^'-^
aiEmaiatrau at to at Q.-I- *F— u a.
3os-S'»-.aa). 3 suits car- at v>
r- -P Ct'F- t. S. r— CO* OOOF— UJ
u-njuiF— -onjo. u.towflujviyat^-'
floi
li,
ai -r- .a
S "O s.
•F— O . ^
s «
•I- . >
F— U) O
Ul U
a g o
c- a. c
o
<^ O) m
X ,]_•
UJ '1—
(0 -0 t.
i-i 3
uj a>
>i O O) J=
&2 S -
< i- +J
at Q. as
F— ui o i—
5 00..^
Sam
S- Q. 3 >
*fc- O) ^
C W UJ
ui '•"• C -f-
jn ta a)
0» 3 C F--
£ W 3 «J
nj o .a ^
c
a>
>. at
O iI'-l-» O
4.) Q r—
"~ B UJ °-
O -P C
S. Q. n3 -O
Q. U 01 O
O F— tj
i&ll
ui at
•r- U
c
a> n
4J 01
•F- U
u
re -C
Z -M
C
sZ
*— 3
VI *t-
(0 at uj
0.0.^
w
£.
0) O)
> ^- ai
O Ul 0) •*—
f-^ 2 1
3 ^ "o.
+J _i £_
C O 4J
re 0) +^ *W
r-J= Ot-F-
Q.+J ^ *—
•aJ
CT J_l
shale (primarily calcium ai
sodium carbonates) absorb i
S02> are dried, and then
collected in a baghouse or
I-H
Q.O 0) -M
•F- CJ ui UJ
a-o ^ uJ*
aia;^.-
4-» 3
4_) 01 g
*j -c 5
ui c at w
ra at t. at
CT E a. i-
electrostatic precipitator
(ESP).
c
o
*4J
M
•£
3
D)
(0
0) •
C
Ul
•2
•r-
s
cQ
3
O*
*OJ
3
f-
Ul
C
0
rtJ
t.
C
01
u
CO
^
§
UJ
•o
c
0)
Q.
+J
1
at
E
O
UJ
0)
(J
rg
E
O
4-
S_
2
•K
sed on information from:
(O
u
3:
0)
^
1,
,
i
1 and Riesenfeld, 1979."
o
1
•
01
1—*
o
PO
2?
i
„
Q.
3
ne and Webster Engineering
o
c/1
1
i-t
^
0)
=
Ul
C
.C
re
UJ
at
L.
u
s.
u
at
UJ
184
-------
absorbed SQ2. The insoluble alkali sulfite and sulfate crystals are then
separated from the regenerated solution in a clarifier and possibly a second
dewatering step such as a centrifuge. The spent alkali sludge is treated by
calcining, evaporation, stripping, etc., which drive off the S02. The S02
can then be converted to a useful form of sulfur such as sulfuric acid or
elemental sulfur.
In the nonregenerable processes, this spent alkali sludge is sent to a
disposal area for land filling.
Dry scrubbing—The dry scrubbing processes use a concentrated slurry of
alkaline crystals which are atomized and injected into the flue gas stream as
it passes through a spray dryer. The scrubbing slurry absorbs the S02 and is
dried by the hot flue gases. The dried spent alkali is then removed from the
flue gas by an electrostatic precipitator or a baghouse.
In the regenerable processes, the spent alkali is reduced to a sulfide
and then reacted with CQ2 to regenerate the alkali and evolve H2S gas. The
regenerated alkali is recycled, while the H2S gas. may be converted to
elemental sulfur in a sulfur recovery unit.
In the nonregenerable processes, the spent material is. sent to a
disposal area for landfill ing. The spent material also may be recycled to
increase alkali utilization.
Hydrogen sulfide control. H2S removal can be divided into two cate-
gories:
• Direct conversion ' :.
* Indirect conversion.
Direct conversion actually oxidizes H2S to elemental S. Indirect
conversion involves removing acid gases (H2S and C02) from the gas stream and
requires downstream direct conversion or further processing to treat the
sulfur compounds. Figure 5,1-5 lists the H2S removal systems available, and
Table 5.1-6 presents a brief description of the process technologies.
Direct conversion—As shown in Table 5.1-6, several direct conversion
technologies are currently available, including Glaus, IFP, Stretford,
Beavon, Giammarcd-Vetrocoke, Takahax, Ferrox and Haines. The conversion of
H2S to elemental sulfur takes place in the liquid-phase in all the processes,
except the Glaus and Haines which are .dry gas-phase removal processes.
Liquid-phase direct conversion processes are ideal for treatment of
gases containing low concentrations of H2S. In these processes, the acid gas
components are absorbed by alkali solutions and then oxidized with dissolved
oxygen to elemental sulfur. High circulation rates of the alkali solution
are required for high performance and to reduce thiosulfate' precipitate
formation. High selectivity for H2S removal can also be achieved by taking
advantage of the higher H2S versus C02 absorption rates.
185
-------
LIQUID-PHASED
SOLVENTS
-CLAUS
•IFP
-STRETFORD ,
•8EAVON
• GIAMMARCO-VETROCOKE
• TAKAHAX ;
•FERROX ;
• HAINES :
-MEA
-OEA
• MOEA ;
•AOIP/OIPA
-DGA(ECONAMINE)
-SNPA/DEA
-SCOT
-BENFIELD
-CATACARB
-GIAMMARCO-VETROCOKE
-ALKACIO(ALKAZiO)
[—DIAMOX
1-CARL STILL. ;
I— COLLIN !
— SELEXOL
— FLUOR SOLVENT
—PURISOL
-SULFINOL
— AM1SOL
-RECTISOL
c
SOURCE= SWEC
MOLECULAR SIEVE
CARBON BED
IRON OXIOE(SPONGE)
KATASULF
FIGURE 5.1-5 HYDROGEN SULFIDE CONTROL TECHNOLOGIES
186
-------
in
at
•c
(0
TJ
a
tn
at
a>
«
y\ ~
UJ C
M as
1 , 1
X
UJ
1—
-J
I—
1
s
t/J O 4J
i— lO
UJ >
»— at
•f- (0 TJ .r- I.
2 u at at it) -P
ui t. _o -P at
•P ' ui -p
S-P C W O
JS •*- TJ U TJ
at cn c o at
S. >r- 4J 3 S- O>
•S^lla >,
V> IB S. U -U S
>>
15
if
cna.
>>
ft.
3
•P 3 .
X to vi
•VS
U) nj
Ot 4«* in
TJ C at
'!•" Of >
o a> S
S, -2- 01
a. at u
TJ
ai
o •
Is
. 3 (0
o
II '
C u)
O QJ
P 13
CM cn
o
M
UJ
0
CJ J3
H- rt)'
UJ . 3
os re
. Q U
i
u
at
at
i
c
o .
-P. U
tO 01
c at
u at •
c tn
. o s-
JZ 'O
a> to
JZ O
c
O OV
lO -
0) -C
U
C M
0) O
I"
Q- O
4-
0
c .
O m
S- -i- (O
o -P cn
**- RJ
N i—
JOJ •£•£
S 3 V
fl •*-
i— f— tn
-f- 3 3
> S r-
tn
•2
at
a.
•||-
in O
tn S
!-"
OS -P
O O -P
• W5 r— C -P
TJ *O E >»
(TJ C «— (0 in
•^ - Of -P 3
t/1 »— fl (O
«^^L O O U f—
x cn u -P o
•g §"s§ £,».
^— -r- C (O
O (O C ^ W> Q.--^-
:^ 4-» at oi 3 e
a. m r— c t. *i- *—
S- 3 OS 0 3 3 4J
O fO >» U •«- CP O
U> ^— i— r— •*-, OJ
^ o o >> 3 *— at
-*
a»
i 2 i -^-o*' :
t "5 !> . 'S . -cg.'^
at c CTTJ c «— o <•— » it- o f— ai'
jzcna>aiaijzn]|4-oi o >r-et03
4J -r- C S- 0) d C3J'r- 4^ > ' . *J -^ > CT
in -F- **- ai •«- +J at o at c o u . >,»— -r-
re a> u m 3 o 3 4) s_ c " 3 at re nj
(J -P O -P TJ Cur— at (J (TJ O» I*- > C. -P
C4OCW1COE— SO Ntn f- OIO
OS-
TJ Q.-P
>i m oi CL TJ at
•p TJ "-a. at*—
. a> e «4-^* 3" 43j3
•^ 3 -r— (O (O
re a. 3 aj at s. o
3> E ' . Q..C £. 4^ Ol 4->
o 4J 3 4-> ai
I- CTOIr-
o cinm CTJC
o 3 o at at u o .
O) 1— , 3 (— Q. 3 C -gy
p- C • • r- ' - f ' TJS -130).
^2Oin 3 OO)OI o O)*»- w>
-p re CU"™ CL'r- O
3 M s- i i— (*_• >t— re 4** •<"
01 1*- oi at. P— o > • i— o > c
01 (— to > J3UOIU. J3UO)OI.
U3cn- o re o « u
Sm s CLint/jo o_ 01 oo c
at<*- 'at retowo (O«J«o
a- TJ o a: cj 013; m cj oix u
i
*-" i — m
u . u c SM § S-
t- S- O (O --5
at at i. T- TJ o
= E O-PC01.OC'|
uai uai aiT-ciacncCT
Ol ^3 inji ^ 3 > r- • C^ «f—
-P i- aj
E-> ^> >a>ojsmocu
Q-tO Q_(O .
« « VI trt
^ ' •* = - =
jstt s ' e '
-p re ' >P nj' • tu at''
£- « ^ > £. £.
tA 4-1 > yj -p S
atcs n c a. &* >P
u o) 'Q. u O (TJ M -C J2 , CO CCOO.
co . s-xi*--Precov» core
O-r-C(0 TJ«*-O O **- . O"-CC
•P-.-PR} >vOO CT O> T- -P re 4J -r- 4-> (tS :
P re v j= *J >> c a» 4-» re r- - -P re <+-
CvTJ CO W V- « Q.TJ C <0 Q.TJ C O .
&. «i— •<— u •<- m o) UI-SM* ^ *r- *f- in s. •>-•(— «
OXC -r-tnTJ>3 OX OX C'TJ
WOO^O 4^>»c:o tnuiOOO inoooc
re a> x ,-P ^-0001301- (oatxc re at x -P o
w 3 « s- p. i. <*- u tn at m 3 o.
vire + i— 4JTJE <—o tn^to+in t/>m4- r-1 s
C*J= O « >» o >> 3 i- .«J= 1. «J= O O
x Q.V) vi UJ=uJ3incxx a. co re x a.v> o> u
-ja - -• " ' - .
tO ' 1 _Q
TJ J3 O Ot
O « S. O X
^ 0 I 0 " JS
i. to re 4-> -ii
-P oi -i— at to
W» _ . CO O > J—
187
-------
^,
-*-». .
§
o
U1)
_J
CD
g
Ul
4)
(O
'c
>
• 'S
(A
Of
3
C
(3
+j
C
O)
t£
3
O -M
r- RJ
41 -tJ
> VI
O)
O
4)
1
J_i
0)
a.
at
o
-c
• a.
Ope rat In
%
a
2*0
c
o at
c at
at nj o
-C -W «J -C
•*•> O Ul r— Ol
c a* n. "~
0 'W 3- 2 *
£ **" ,_ £
uj ui nj nj.
S- U) O O .
• 3 t. O 4= O
0 ,
4) "O
i- 3 C
at TJ ra
o o
c .Jj'+j
O) -r- *—
§£3 .
i, t. ui ui
O. 3 C 4J
x -o o
.2: I3 3 o
S- >»TJ 43
(d i. at RJ
S 13 s. r-
Ul
C
,2
Q. C
O •— C
<*- Ul rtj
3 at at
01 !- Q.
u. « o
X*
0
03
I
OV
IT)
CO
t
'SS'S
o*
•p- -r C
13 W4J «
(0 P— 3?
e o a
c o S3
o -i- a>
..P- -W ,rtj U.
o TX 'r* ra
ui O O
ca at x o
ui S
x
o
t
41
U_
Ui
•o c
at o
C • Ot S- '
"1 It
o
Ul
- o '«
o
e.cj
o . -
£ *0' C
S. 4> +J
O
+J O
5-58
rtj
«J
C
C (0
c
flj C
r— O
,2 S"
a. o
V)
= .
4)
r- O
3
O C
O
at .r-
S2 .
(/»•$•>>
at c s
3 s a
OS O V
«-«!&
x cL*p£
>-*C *j "*
S U» (O (0
at at *>
S- Ul 1. C
.p. at
(A "OS
> CJ at e
s- tl o
42
S- /— Ul
a. c
U) Q. O
O -*J
O) (O
(0 d-M
V) rtj O
o
I V 04
,2 ,,3
O 1-
x rtJ "O
at a> c
>1 «
4-»
go N
•*- X
*« >» at
•Q 4» O
a» > e
2 Ul £.
V>
4) C S
o w a.
as wen
fl3J= §
-O c
Ol O **
t.r- (O
4->
•i 2*1
and C02
enerable
oethahol
V) Ol C
N 41 O
X S. E
LU
E
8'
4-)
3
'E i
a)
s- -a
.J:S
LJ
*O *p-
e ui
RJ ai
-C
= -
fl C
(0 U)
S *>
f
C -P
•r- O
at
t. Ul
at
C 0
13
s.= ^
•^Si
-*J *j
C O VI
•p- 3
§c ja
RJ S-
T5 e o
at ut
a. o w
'i- I Ol C
4Z i ta
at O)r- C
•r- .C S- O O
O 3 C CJ
•0^=^=°
at c a> 01 u>
t.- 4) t. -P- C
,S- S 3 ,£ O
at at a» •+•» to M
•&.£.{. *p- £. CO
V)
^
"*_
O
*m
i
+J C
>*•*- ai
43 S ••-
T3=f
o» o nj
t. •»•» 4J
O O fl
43 O> 4)
fl3 S- C *
Sr— (O t.
43 •— 3
fl3 O +J
•o t. c ra
c at ns t.
fl C 4= 4)
x s- o +J
^3
o
at
^ o
a ut
s fi-
ai
at at
at s-
S s*
.a at
Is
11
• c
-V *
4*> Ul
at
v» c
x s -
o
£-
> a
-M at
o u>
at
P= £_
at o
Ul
I- 2*
ai Q
x a.
c
o
21
a. t.
w
• — UJ
o o
at i.
o c
.3
Ul
^"S
o **o
r- O
|l
•«1
ClfO
VI
£.2.1
= S5
o at o
Q. 41 4=
o-o *
43 i. -O
:§i
!!1
vt^'s
43
R)
LU
£
i.
**—
fu,
O 41
•i— at
§• c
C Ul
-0
>
E O
£. ui
VI C
= 1
o
o *>
ai ui
VJ VI
C 1
o §
0
a>
C 4->
rtj O
4= 3
•*-> i-
E °
V)
M
at
p- o
•fJ 4J
S =
o
5^
fi.
ui *J
II
as u
v>
5.2
0 '5
cM
O 41
a. «
II
m at
§1
•»-» s.
o
at >
V) 43
JS
"s
a
"x, ,
3
"o s
o at m
s. at ui
-a
> •
1
V
oi
c
1
1
a.
o
-U)
a
'S
4= V)
•P? 30
Ul CM
. a»o
-C — J V OJ
at s 4i
2 ,
<0 >» C 4)
4-» O S-
U> *^> *P- IQ
Ul •(- p— u
jf
a>
u
0 C
t- o
Q.-r-
ui ra
RJ i-
Ol 4)
SM g_
^°
«.?
VJ
X
**-
o
*«
8
s •
ra -3
£§
« U
^ £ *
o c
at -P^
C r— S
O'43 <3
*J S. *O
1111
«C.2.Q
I
=
C
3 LU
C} "*-*
Ul C
j_ >P-
3 (B
CB U)
II
at m
1
188
-------
Disadvantages
Advantages
Development
Status
g
|
O)
' Q.
Operating Principle
3
o
22
c
c u
O 0)
tJ h-
High pressure process
i Vacuum distillation
probable.
5s»
"3 w "E
'f- 0 <» .
§ O.+J C
rtl O i- .Q
^ O t- £.
COS and CS2 are not
to the solution. De
products removed by
through activated ca
-C
Widely accepted
choice for the
treatment of hig
pressure natural
i/>
M
S
O.
m
o
!
i
Process utilizes experience
gained by SNPA in using DBA.
J3
w
Q
o.
25
t/1
JT
O)
Ul
Ol
t/i
m
01
concentrations o
Ul
acidic component
01
J= O)
•U C
OIPA removes -30% C02
which is recycled to
Claus process, diluti
the feed.
Ul
3 4-»
O
a. s. .
§5 §•
Removes all sulfur c
Specifically suited
Claus tail gas clean
r— C
ro o
Several commerci
units in operati
since 1972.
CM
O
Jj
0)
*J W
' 3
O C
o
^ -M
** 2 >
u» *J E
0) C O.
1 i °*
as tj rn
M
Process uses DIPA to absorb
H2S from the Claus tail gas.
Non-H^S sulfur compounds are
converted to H^S before
absorption in OIPA. Regen-
erated H2S is oxidized to SO
before venting.
J3
\
V)
High pressure process
(U
Ul (A u)
'= "S ?r~
High temperature pen
of highly concentrati
tion. Process is ve
COS, CS2 and RSH eas
removed.
.u
c
(U
Process utilized
worldwide, with
further developm
in recent years.
m
S'S
4— (t«
O O
as m
o o
w &f
11
il
01 rH
Process uses hot (190°F)
i potassium carbonate to absor
C02 and H2S. Regenerated by
pressure reduction.
5
X^ Ul
m mo
•— o fl •
a a. c
. •»- o
*^- -w ^
cot.
a s a
ca >«^o
High pressure process
V)
| 3
O r—
r— (Q
C 5
Higher gas purity am
steam consumption th<
Benfield. Lower cap*
c
o
Plants in operat
worldwide.
to
X
^
0)
3
O C
o
j=£
4-) fl3
U> -*J >
Although operatd
abroad since the
1930' s, no known
commercial insta
lations exist in
U.S.
X
.
0)
*— O
3
o e
M **
** if
«» e s •
u eu a.
3 u a
01 g in
OS U V
Ul tJ
Process uses various pro-
prietary absorption solution:
. of alkaline salts and organii
acid.
4r •• *~\
o a-a2
U *i— N
i- nj ^
> < **x
-------
Disadvantages
vantages
3
Development
Status
S
O
Q.
u ,
2 c
CL"-
•i— 3
U
5- C 1)
i "" o"
u c uu
v>
z"
^J
3
o c
o •
Jr'£ 1
•*•» at Q.
u t. •— 3
a o u o
t/» &• S-
> a: -~ cn
U Cft*— 01 •
VJ 3 -W U»
C
£2
o
VT 2.
, ** -Co
1!
• f O
ui a;
0) S-
i. 3
•i— U)
3 ui
cr a»
OS CL •
3
' -2?£
^ 3
IB Ul
(fi C
a. to
. 2*
C T3
0) C
> 03
O VI
"Sw
u "a
•i- Ul C
X 0> 3
S> 0
o a.
Z I- O
I ul
s- en- r-
a.r— o o
Few plants in o
tion for natura
treatment and f
synthesis and c
derived gas
purification.
to
01
Z
0)
i— O
s"§
.§'.*»
E- •'
01 C S
u , 3
c o 'i- u ja o
CO £ ftj " JS
CO t. 3 TJ •»•>
1.0* ui 01 •>-
°S'5S§:S
Ul 01 O r— •<—
«
= , - .
a>
i°
o c
o
f -fj
4J 03
2 "c s
o aj a.
S« 0
CR R3 Ul
£. U Ul
. O1 'i—
U-S'
Uses an anhydrou
solvent propryle
which physically
acid gases.
4->
C
1
o
V)
1
u_
T3
C ui
Ul <0 T3 •*-
t. *> y 0)
3 c m i.
Operating tempera
must be near ambi
a certain minimum
gas partial press
required.
r •" •
c
1 <0
&• cn
m u
CL O
"U
is
.•s«
> o • •
•f-U ui
*J -d
U Ul C
a - c e c o
O 01 Q. 01 >
•gS°-St ui
£- Q. u)
O 1 •"
M -0
Ul I
Uses an anhydrou
solvent H-methyl
which physically
acid gases.
.a
m
o
Ul
*£
3
Q.
S- > £i
3 (O U)
Ul 0) (13
Ul .£ i—
Optimum operation
requires high pre
Solution absorbs
HC's» requiring f
>,
u cn
as •(-
Q.JC
as
"A%
C O 3
(O C Ul
S"3 Q.
Ul
Ul I—
4» >
Wide applicatio
the treatment o
natural , refine
synthesis gases
CO
z
S 3
5S «
3 O
O C U
O
0) «P- TJ
£ *» C
» IS (TI .
W +^ "> S
u >
E O •
Sis' •
S ta ra
ta ^*'o
0) >-• 3
ui O ul
•°.
rtJ
o
c
2r
VI
tank separation.
—
vv
Nonselective for 1
i
|
> ui
O TJ
§3
O
<*- §"
O O
O U>
as c
CJ -f-
S- 4J
S s-
5 c.
o o
•^: c
Ul Ul
O O.
VI
«
=• s
<— o o
4J *J CJ
o c -a
o e
0) •»- to
& -t->
3 S (-J CV
•o c .
o) o o tn
OS O V V
u
JS
"Ix-
4» 'Q.f—
0 Ǥ-
<1>
O) UJ r—
ui S 0
3 ^ ui
3
O
Ul
e
1
S-
O)
ui' cn
. (U *F»
Complex operation
High solvent lossi
Best suited for h
3
a,.?-
Ul CO r—
3 +J flj
U -r- VI
2 ui S
°"-£
3 3 .
0,-U 01
C (S C
^~ 01 !£
•w a yi
X -P C
ul >
Thirty-six plan!
are in operatioi
worldwide. Twe'
>t 0)
ti— -f
i. U)
**. o «
•i- mat. u>
f— *O O nj c
m £. f— m
r- Q. 3 4J
3 »«- u a.
*»— o -C a> »^ C
J •— o
FX m o aj 01
UJ x- ' Q.T3 OS
•*- s
'at <*-
M tn
^o,3
'S 'S «
O 0> ifl
r: s. CD
z
+J
o c
o
•M (Q
£ .
li&
OS U V
s
Ul Ul
d) "O
.,- o
ui a.
Use of nvolecxilar
adsorb sulfur coo
3 m
Ij gj
|ni >
i— 01
E v>
190
-------
4
o
*
*fi L
t
i— i
in
00
f2
Ul
O)
S1
4-)
C
(0
1
' S-
O> '
01
nj
"c
RJ
1
-P
<=
4>
O 4->
!«
a
Ol
EJ
C
m
i
-2
1
Operating Principle
0)
o
o *o
II
"S -,
4-> >
e s. to s
.2 5 .2 S
-P r-i
4) U > §" C 0 TJ
4J i— O O O lO
0) C X O) -P
•" >•§!"' iTi
§ 5 £ 1 3 "S r
.a -i- 3 w u
« « ai c *3 s- IN
O S. S- rtj Ul CLX
TJ
1
(O
-Q
Q •
Ul RJ
O
S. S
3 41
4* S-
U) PJ
3 -P
Q. 01
di ~ '
> O
C
o
•— 4->
•r- S-
U 4)
C ° 10
U
Ul 4)
_>»-P J=
X (O
wi a—
tn
X
4J
* -
": 9"
•4-> -P
3
P §
£ 4J
"*"* 2 >
a) c a.
MS0-
T3 C P4
a: u d
? • ' •
U 1
•r- «— flj X
Activated carbon cataly
oxidizes H2S to element
sulfur at ambient tempe
tures. SuVfur removed
solvent washing.
•a
m.
"S
m
a
3
^ rt
I Is
i— «S X
O « wi •
> Ul O TJ to
O
Ol, S
j_ Ol
u) 4) -
01 -P
u ai
P •».
1 1
— J O'
41
O)
£.
ffl
Ul IQ
: Ul (d O
03 {j
U C 01
o o .c <*—
i- 4J o
Q.TJ
a> s- -p
TI ui O C
o="-l .
r- 01 «P ui
i- •?- (5 at ui
41 4J U !_ (O
> Ul Ul 4J 0)
CO
X
4J
at
r— O
4J 4J
3
0 C
£ -p
4-» rtl •
Of C O.
ss°-
TJ C rt
01 "i
x n
> O « 4. O
<— W»-r- M
a» £ u. ^° x*1^
§C +. ui 01
0 .01 .
OJ -f- C7 N 4.
t. *J 0 . *r- 3
O «O TJ *^
VI RJ 01 iN-^ r—
« 41 U. X X 3
X S- cvj to O u)
.a •—*
- Of
C Q
s£
01
' =§
O u) .
•r- UT
ui -C ui
2ii S
o 5 S
O 4J Q,
1'iJ
UJ W) **-
C 0>
lii
to s. o
CJ 0.4-
3
*C
ra
(0
rtj
41 4)
U -P
3 m
TJ *t-
O, u)
C
?— • -2
ra -fj
u £
§0.
o •
S Ol
O C T)
HI
(« C O
-J 3 S
U)
="
W
u
•— o
3
0
w 2
S e S
u a.
fu Q.
o **•
a: u v
j.
4-1 «) 1
Air and preheated gas w
H2S catalyzed to form S
which is absorbed in an
aqueous ammonium sulfit
bisulfite solution.
^
3
u)
H
0)
,0
O) •
C Ol
§?""
*" S
0 X
' C 01
Ul V)
O TJ'
C C '
^
(_
nj
o
4J
0)
t
o
3
s- c/i
> x1
J
R3
1- O>
c Q"
O C OJ
U 'r- "13
TJ ui 5
TJ fl3 S-
C i— O
= 0.3
i~* C
41 rtj O
O O -P
wi
04
x
•p
ai
-p -P
3
o c .
oi.2 i
4= *J a.
•P (t; a.
0) G10
30?
i§s
CB
(O C t
f .4d VI
OJp" M
3 3 X
2.8 *
i'il
U (J
W> C (0 .
•i— i— 0) O
M i. «
m %- 01
JTJ tO
a> c c
t— .0 -r- ISJ
(Q
i
i
u
c
rsj
sed on information from
vo Corp. » February 1976
1 and Riesenfeld, 1979.
rtl (O -C
-Q S. O
U
u nj xi
Ul
O
VI
191
-------
The gas-phase direct conversion (Glaus and Haines processes) consists of
thermal oxidation of one-third of the H2S to S02, followed by; a series of
catalytic reactors that react 'S02 with the remaining H2S to form elemental
sulfur. The heat for combustion in the furnace is obtained from the oxida-
tion ,of H2S; thus, the H2S concentration must be high enough to sustain
spontaneous combustion. Therefore, the gas-phase conversion requires an acid
gas stream with a higher H2S concentration than the liquid-phase conversion.
Indirect conversion—There are essentially five classes, of commercially
available, indirect H2S removal technologies that are used- in conjunction
with direct conversion technologies; these are, removal of H2S by:
I. AlkanoTamine .
II. Alkaline salts " ' .
III. Aqueous ammonia
IV, Physical solvents
V. Dry bed processes.
The alkanolamine processes (I) remove acidic impurities, i.e., H2S, C02,
COS-, and CS2, from gases by an acid-base chemical reaction with the amine.
The process involves an absorption-regeneration cycle of a circulating amine.
Commonly used amines are monoethanolamine (MEA), methyldiethanolamine (MDEA),
diethanolamine (DEA), diisopropanolamine (DIPA) and diglycolamine (DGA).
Major equipment systems used in the amine process are a gas-amine contactor
(absorber) for absorption of the acid gases and a regenerator (stripper) for
releasing the acid gas from solution. A downstream sulfur recovery facility
is required to oxidize, or recover, the H2S. '
Alkaline salt processes (II) use an aqueous solution of a buffered
potassium salt. The weak alkaline solution absorbs the acid gas components
of the feed gas. The process operates at medium to high pressures because
the absorption capability is influenced by the acid gas (H2S and C02) partial
pressures. The alkaline solution is regenerated by reducing the rich
solution pressure to near ambient pressure, followed by steam stripping and
sulfur recovery.
'••' '
The ammonia process (III) uses the same mechanism for H2S removal as the
alkaline salt process (II) except the ammonia is used as the absorption
agent. Regeneration and additional sulfur recovery are necessary.
Physical solvents (IV) have low heats of solution and can absorb acid
gases in proportion to their partial pressures. These processes require high
acid gas partial pressures which are achieved at low gas pressures and high
acid gas concentrations, or at high gas pressures and low acid gas concentra-
tions. Physical solvent processes are most economical when the feed gas is
at high pressure and bulk removal of the acid components is desired. A high
degree of selectivity of H2S absorption is possible, but additional equipment
is required, increasing costs. A downstream sulfur facility is also
necessary to recover the H2S.
192
-------
Dry bed processes (V) generally employ two techniques to remove H2S from
a gas stream: (1) adsorption onto a dry bed, such as a .molecular sieve or
activated carbon, followed by desorption of the H2S from the bed using a hot
gas stream; and (2) reacting the H2S with a dry bed material such as iron
oxide to form a solid sulfide compound, which is then oxidized by air to
regenerate the dry bed and to form elemental sulfur.
Sulfur Control Technologies Analyzed—
The prime sources of S02 emissions from the TOSCO II plant are the fuels
consumed in various unit processes and auxiliary facilities. ' All of the
gaseous fuels except the C3 fraction (Colony had planned to market this
liquefied petroleum gas, or LPG) are used in the plant. In: addition, a
portion of the crude gas oil product (before upgrading) is combusted in the
ball heater, thermal oxidizer and steam superheater.
According to Colony's PSD permit application (Colony Development Opera-
tion, 1977), the TOSCO II preheat system is capable of removing 95% of the
S02 from the ball heater and thermal oxidizer flue gases. Furthermore,
the amount of S02 in the steam superheater flue gas is fairly small. If
these conditions exist in a commercial operation, then there would appear to
be little need for removing the fuel-based sulfur from the gas oil in order
to reduce the S02 emissions. From the processing viewpoint, however, the
sulfur is removed from the net oil products by hydrotreating, but this is not
considered a pollution control measure for costing purposes in this document.
The sulfurous gaseous streams from the retort, foul water stripper,
ammonia recovery unit, hydrotreaters, and delayed coker are treated for
sulfur removal. The most significant compound of sulfur in these streams is
H2S (although COS, CS2, and mercaptans also have been reported),; therefore,
the technologies examined are based on removing and recovering the H2S..
Since the H2S is recoverable as salable elemental sulfur (as proposed by
Colony), flue gas desulfurization technologies were not analyzed in detail.
Two separate H2S removal and recovery processes, based on the informa-
tion provided by Colony (Colony Development Operation, 1974 and 1977), have
been examined in this manual. These systems are:
• DEA/Claus/Wellman-Lord
• Stretford.
Both of these systems have been used in oil shale related industries at
a scale necessary for the TOSCO II plant. The individual technologies in
these systems have been proven to be technologically and economically
feasible, and substantial cost and design criteria are available in the open
literature and from the technology vendors.
The amine process (alkanolamine process I) proposed by Colony to
desulfurize the retort gas is the DEA (diethanolamine) process.. It removes
approximately 99% of the ,C02 and all but 135 ppmv of the H2S from the retort
gas (Colony Development Operation, 1977). The acidic gases in the retort gas
193
-------
are absorbed in the DEA solution, and the rich amine stream is regenerated in
a steam stripper column and returned to the absorption column. The stripped
acid gases (primarily H2S and C02) are treated in a Claus unit for sulfur
recovery. This high removal of C02 is not required for LPG ;and fuel gas
production and it increases operating costs because of the large quantities
of steam needed in the stripping (regenerating) section of the.process. An
alternate amine system using MDEA (methyldiethanolamine) is highly selective
for H2S removal. This selectivity allows a reduction in steam;requirements
of approximately 20% as compared to DEA and, consequently, reduces operating
costs. .
The stripped acid gas stream leaving the amine unit is approximately 14%
H2S by weight. This stream and overhead gases from the ammonia recovery unit
and foul water stripper are treated in the Claus process.
In the Claus process, the acid gas is blown into a sulfur burner where
it is mixed with sufficient air to oxidize one-third of the H2S to S02.
Portions of the other organic sulfur compounds are also converted to S02
during combustion. The S02 and remaining H2S enter a reaction furnace and
then pass through a three-stage catalytic reactor where they 'react at 95%
efficiency to form elemental sulfur. A higher conversion efficiency is
attainable with additional catalytic stages. The unreacted S02 and H2S are
sent to a Wellman-Lord tail gas unit.
In the Wellman-Lord unit, the non-S02 sulfur compounds in the Claus tail
gas are converted to S02 by incineration. A majority of the: S02 is then
absorbed in Na2S03 solution, while the remainder is vented to the atmosphere.
The S02-rich solution is regenerated by steam stripping and the desorbed S02
is recycled back to the Claus unit for further recovery. An S02 absorption
efficiency of 92% is assumed for the process, but higher efficiencies may be
obtained by increasing the contact time between the reactants. Both the 95%
efficiency for the Claus process and 92% efficiency for the We11man-Lord
process have been specified by Colony (Colony Development Operation, 1977).
1 • • •
The other H2S removal system examined is the Holmes-Stretford process,
which has the capability of treating gas streams with low H2S concentrations.
The Stretford process is a liquid-phase direct conversion system which
selectively removes the H2S and catalytically converts it to elemental
sulfur. The process is capable of reducing the H2S in the treated gas stream
to 30 ppmv. Appreciable amounts of carbon dioxide and other non-H2S sulfur
compounds are not removed by the Stretford process.
Tables 5.1-7 through 5.1-9 give the major' equipment lists for the DEA,
Claus, and Wellman-Lord processes, respectively. The major, capital and
operating cost items for the Stretford technology are presented in
Table 5.1-10. The cost of sulfur control in the TOSCO II plant, using either
the DEA/Claus/Wellman-Lord processes or the Stretford process, /is presented
in Table 5.1-11. Figures 5.1-6 through 5.1-9 provide cost curves that are
specific to the design ' of the DEA, Claus, Wellman-Lord, and Stretford
processes examined in this manual. Process descriptions and stream composi-
tions for these technologies are presented in Sections 3 and 4.
194
-------
TABLE 5.1-7. MAJOR ITEMS IN THE DEA GAS TREATING PROCESS*
Capital Cost Items
Operating Cost Items
Absorbers (5)
4' diameter x 70'
Regenerators (4)
12' diameter x 70'
Flash Tanks (8)
7' diameter x 21'.
Surge Tanks (8)
7' diameter x 35'
Reflux Tanks (8)
3'6" diameter x 14'
Lean Amine Pumps (8)
1,619 gpm @ 200 HP
Still Reflux Pumps (8)
135 gpm § 10 HP
Lean DEA/Rich DEA Heat Exchangers (4)
66 x 10s Btu/hr
Still Reboiler Heat Exchangers (4)
106 x 106 Btu/hr
Amine Reclaimers (4)
10.6 x 10s Btu/hr
Still Condenser Aerial Coolers (4)
66 x io6 Btu/hr
Lean OEA Aerial Coolers (4)
29 MMBtu/hr with a 558-HP Motor
Site Preparation and Foundations
Piping
Electrical
Instrumentation and Controls
Painting
Diethanolamine (DEA) Makeup
65 gpd
150 psig Steam
330,750 Ib/hr
Process Water .
368 gpd
Electricity :
2,930 kW
Manpower
h Operator per Shift :
h Supervisor on the Day Shift Only
.* Design basis: 6,700 ACFM.
Source: SWEC estimates based on information from Maddox, April 1977.
195
-------
TABLE 5.1-8. MAJOR ITEMS IN THE CLAUS PROCESS*
Capital Cost Items Operating Cost Items
Reaction Furnace Boiler Feedwater
43 gpm
Combustion Air Blower
Electricity
Waste Heat Boiler 825 kW
Catalytic Reactors (3)
Sulfur Condensers (4)
Reactor Preheaters (2) ' >
Sulfur Rundown Tank
Knock-out Vessel
Piping
Electrical'
Instrumentation and Controls •
Site Preparation and Foundations
Painting ,
* Design basis: 14,500 ACFM, 173 LTPSD sulfur recovered.
Source: SWEC estimates based on information provided by Pritchard Corp.,
September 14, 1981. • .
196
-------
TABLE 5.1-9. MAJOR ITEMS IN THE WELLMAN-LORD PROCESS*
Capital Cost Items
Operating Cost Items
Stack
8' diameter x 210'
Package Boiler
50 x 106 Btu/hr
Spray Tower
16' diameter x 20'
Spray Tower Condenser
2,600 ft2
Spray Tower Recycle Pumps (2)
• 2,220 gpm @ 50 HP
Liquid Vapor Separator
11' diameter x 17'
Absorber '
14' diameter x 40'
Absorber Recycle Pumps (4)
61 gpm @ 1 HP (2)
47 gpm @ 1 HP (2)
Surge Tank
14,000 gal
Surge Tank Pumps (2)
19 gpm @ 1 HP
Evaporators-Crystal! izer
4' diameter x 12'
Evaporator-Crystal!izer Recycle
Pumps (2)
12 gpm @ 1 HP
Evaporator Heat Exchanger
200 ft2
Evaporator Condenser
400 ft2
Na2COs Makeup
1,728 Ib/day
Antioxidant
29 Ib/day
150 psig Steam
19,170 Ib/hr
Cooling Water
5,760 gpm
Makeup Water
2 gpm
Fuel
83 x 106 Btu/hr
Electricity
56 kW
Manpower
1 Man/day
(Continued)
197
-------
TABLE 5.1-9 (cont.)
Capital Cost Items Operating Cost Items
Evaporator Liquid-Vapor Separator
1" diameter x 4'
Dissolving Tank
14,250 gal
Feed Pumps (2)
30 gpm @ 1 HP
Storage Tank
6,400 gal
Absorber Heat Exchanger
630 ft2 . ,
Weighing Belt j
!
Piping :
Electrical '
Instrumentation and Controls . "j '
Site Preparation and Foundations i
Painting • ' ,
. " ........ ' i
* Design basis: 25,000 ACFM, 173 LTPSD sulfur recovered in the Qlaus plant.
Source: SWEC estimates based on information from U.S. EPA, January 1975.
198
-------
TABLE 5.1-10. MAJOR ITEMS IN THE HOLMES-STRETFQRD PROCESS*
Capital Cost Items
Operating Cost Items
Knock-Out Drum
10' diameter x 22'
Absorber
18' diameter x 75'
Oxidizers (7)
37' diameter x 62'
Pump Tanks (4)
37' diameter x 50'
Circulation Pumps (5)
20,000 gpm
Flash Drums (2)
20' diameter x 50'
Slurry Tanks (2)
35' diameter x 50'
Slurry Pumps (4)
430 gpm
Filter Systems (5)
8,500 Ib/hr
Sulfur Melters (4)
4 x IO6 8tu/hr
Sulfur Decanters (4)
5' diameter x 171
Sulfur Storage Pits (2)
4 x 10s Ib
(Evaporators (2)
6,000 gpm
Heater/Coolers (4)
Heating Duty = 10 x io6 Btu/hr
Cooling Duty = 5 x io6 Btu/hr
Plot Area
49,000 ft?
Holmes-Stretford Mix
760 Ib/day
Soda Ash
15,222 Ib/day
Process Water
65 gpm
Steam
4,500 Ib/hr
Cooling Water
225 gpm
Electricity
18,600 kW
Manpower
2 Men/day
* Design basis: 6,700 ACFM, 173 LTPSD sulfur recovered.
Source: SWEC estimates based on information from Peabody Process Systems,
Inc., February 1981.
199
-------
J
s.
f™
§
o
)— •
H-
_J
_J
O
o.
Q£
u_
=J
1/1
!£
^-
O
21" o o
u «•
03 •{->
3 tn
e o
c u
•
01
• C s^*
•p- tn
to 0
i— i- 13
IB 0) O
*> Q-*f>
0 0>-<
I—
to in
3 O
c o
c
o
u
in
a>
•p"
•§
+j
0)
tn
to
U
S £-
« JS
S- £
SJ:
*D
00
A
s
2
CM
r-t
P-*
O
O
cn
in
4-£>
XI
4->
C
•
IT)
r-l
CO
cn
CO
CM
in
CM
r-l
O
S
ID
<*D
ca
U)'
HI
•p—
•o
3
-U
01
tn
1O
o
f.
s
01
°H
si
S!
(Ol
-J
tn]
1
§1
H
in|
c
tu
E
to '
HI
i—
•a
c
to
>>
s-
o>
o
u
cu
o:
in
10
•a
s-
&
IO
S-
+J
u
^^
in
CM
o
CM
s"
CM
I-O
in
o
o
o
CM"
tn
u
j *
Ul
II)
tn
10
U
^>
1—
O
1—
tn
o
u
P_
o-
£.
c
o
u
10
3
c
to
ID
O
n>
(-•
4*^'
0
Q
'5
5
3
a,
u
c
o
tn
•p-
to
a)
•o
s-
o
ID
C
0
•r-
U
IV
Wl
a
CO
IO
—
f""
2
c
o
c
0
3-
^~
o
Q.
c
10
s-
i.
U IO
tO Q.
1. 0)
f- S-
Q.
o in
52
0 0)
+J +J
HI 0)
5 3
m 10
20
CD
4^ O
V 4J
10 T3
Q. O)
C U
0) U
3 3
P— T3
22
a.
h™ Q
U
LJLJ
.31
•Q
•a
•o
^
o
s.
a,
c
o
'5
g
o
t^-
c
o
•o
01
tn
10
in
HI
4J
10
£.
•p-
in
0)
p-l
C£
^
.
a>
a
&
200
-------
9OI % '1SOO 9NUVU3dO "iVflNNV 133810
e\j
oo
<£>
\
\
CO
u
o
a.
-------
£OI $ 'ISOD 9NUVM3dO "W1NNV 13381(3
8
(VJ
si
CJ CO
o
a
az,
to
LU
O
o
eg
a.
o
£
to
CO
o
c
a
0)
to
(O
3:
>-
O
o
ce.
u.
_i
3
to
u_
o
s
UO
LU
u_
OI g '1SOO IVIIdVO Q3X1J
202
-------
gO! I '1SOO 9NU9H3dO 1W1NNV 103810
'*'
CM
LU
o
§
cu,
Q£
o
CM
O
O
CM
O
00
s
o
LU
£
o
(J
a:
u.
CO
o
CM
9OI '$ 'ISOO IVildW Q3XIJ
S
01
TJ
1
a,
(O
2
o
<*-
o
T3
ai
in
m
o;
a
LU
O
o
o
to
o
o
oo
i
LU
LU
o
O
203
-------
9OI JK 'J.SOD 9NIlVH3dO IVflNNV 1D3UIO
o
CM
si
«M CO
|
3:
cT,
O UJ
GO Of
UJ
a:
o
to
UJ
CJ
a.
tie.
e
o
to
m
o
IT)
CD-
'S-
9OI % 'iSOO IVJLIdVO Q3XIJ
u
•o
I
o
a.
c
o
ra
o
4-
c
"8
Of
o
tu
u.
o
8
i-«
in
ijj
on
CD
I—«
Ul
O
ae
o
to
204
-------
9OI £ '1S03 9NIJ#H3dO IVDNNV 103810
o
(VI
CVJ
s
co
to
LU
O
§
LU
ce:
O UJ
CO (£
UJ
cc
to
CJ
o
CO
UT)
o
tr>
o—
gOl % 'iSOO
Q3XIJ
o
a,
o
*i*° .
•*•»
(Q
O
O
T3
01
u>
(O
cc
a
LU
o
0£
Q£
U.
S'
JJ_
s
(jj
LU
204
-------
Other Sulfur Control Technologies Analyzed—
In addition to the DEA/Claus/Wellman-Lord processes and the Stretford
process, the Shell Glaus Off-gas Treating (SCOT) and methyldiethylamine
(MDEA) processes were analyzed. These technologies have not been proposed by
Colony, but they may be applicable to the TOSCO II retort gas. ,
The SCOT process can be used as an alternate for the Wellman-Lord
technology, while the MDEA process can be used as a replacement for the DEA
and We11man-Lord (or SCOT) technologies. ;
The SCOT technology has been developed specifically for the Claus tail
gas cleanup. The sulfur species in the feed stream to the SCOT unit are
first converted to S02 by incineration, then to H2S over a catalyst in the
presence of a reducing gas. The resulting gas is cooled in a quench tower to
knock out moisture, and the H2S is subsequently absorbed in diisopropan-
olamine (OIPA). The clean gas is incinerated and then vented to the
atmosphere, while the rich amine is regenerated by steam stripping. The
H2S-containing overhead vapors from the DIPA regenerator are recycled to the
Claus unit for further recovery of sulfur. A removal efficiencyjto ^300 ppmv
H2S in the fuel gas is obtainable with the SCOT technology. The DIPA-
solution absorbs approximately 25% of the C02 and recycles it :to the Claus
unit. Figure 5.1-10 presents the flow scheme for the SCOT process.
The material balances for the Claus and SCOT processes, when applied
specifically to the acid gas from the TOSCO II plant, are given in
Tables 5.1-12 and 5.1-13. The treated fuel gas is used as the reducing gas
(a substoichiometric amount of air is used in the line heater to oxidize the
fuel gas to CO and H2 which then react with S02 to produce H2S and C02). To
avoid the H2S odor problem, the SCOT flue gas is incinerated before it rs
vented to the atmosphere. Table 5.1-14 contains the equipment breakdown, as
well as capital and operating costs, for the SCOT process. A cost curve for
the process is presented in Figure 5.1-11.
The MDEA process is selective in removing H2S from a gaseous stream when
appreciable quantities of C02 are present. The DEA process scrubs out
practically all of the C02 at 30 ppmv H2S level in the treated gas. On the
other hand, the MDEA process at the same H2S removal efficiency ; absorbs only
30-40% of the C02. This selectivity results in a significantly lower steam
requirement for. the MDEA regenerator. In addition, the acid gas stream is
smaller in volume, resulting in a reduction in the size of the downstream
treatment equipment. The acid gas is also higher in H2S concentration;
therefore, it is more suited as a feed to the Claus process.
A process flow scheme for the MDEA technology is presented in
Figure 5.1-12. The operation of this process is similar to the DEA or any
other amine process. The acidic gaseous components such as H2S and C02 react
with the amine to form rather stable sulfide or carbonate salts; thus, they
are retained by the amine. Other gaseous components pass through the amine
unreacted. The rich amine solution is then regenerated by steam stripping,
where the salts are decomposed back to the amine and the acid gases. The
lean amine is recycled, while the acid gases can be treated further.
205
-------
/\ /\
3
oco
ao
^- '
CO O
diS
CO
u>
UJ
u.
3
u
5•
•« «» a
o:
£UJ „
w u. u?
£
^
ts
s s
a:
CO
=> -J en
dSS
d«
£ »
^ j
ut g
si
w
0
o
m
CVJ
— '
CVl
evj
O
CNJ
1
ev
ll
d
, •
to oo
UJ ^
^s
CJ —
= . is
S j= •0>
ro 10
S 2
S ii !
35 •
u. ce
O
(O
!
0'
z
d
z
o
z
ci
z
to
a
•?
g
eg
o
<
u.
o
oT
UJ
t—
O
-------
w>
o
§
0.
J3
3
o
LU
jE
a:
o
LL»
LU
CJ
«s
2
w»
3[
OB
Ul
t-
*•
1
•
t&9
Ul
1
1—
&.
^>
f
i— C
m «t-
-l-> U
o c
h- t— i
C
0
•r*
S. S.
C<
•i—
U
c
>»
O)
>
0 T3
O (0
i.
it!
c o
o
^
Ul
as 00 1 1 Cft
f-l 00 1 CO rH O» 1 1 ^f
«>. Ifl - * ' 0 0
•* * cfT
O pH CM
co
CD
«4
I-i
CM if) i «* o co i i en
10 co t co o en i i ^>
co^ 10 «* co o
r-4 r-( O CM
r-l
co
co
in*
nj
ii i i o in rH ii
ii i i * r» co i i
CM O CO
orT oo"
10
s.-
co"
co
in i i i CM i i 10 i
co i i i r*« i i LO i
CO i— 4 •
LO CO
CO
m
co
CM 1 1 O CM 1 1 1 |
cn i .1 t— 4 LO • i i i i
CO r-f CO
CM
*f
in
ea
CM
rH l O O •* 1 1 l|
oo i to co cn i i i i
CM_ CM rt
CM CO*
r-l J^*
m
i-t
CO
es"
en
*' * o * eo co ' cw rs 'o
CO«J «3
Ul
-Q
Ul
+J
It)
u>
O
LU
OO
••
U
i.
o
-------
(/)
I/I
1
LU
U.
S BALANCE
MATERIAL
S
ui
LU
CD
i.
J2
3
O
U.
U)
c
V) •»-»
5£. 03
01 U
4J 01
£ C
- c
o
01 *r-
c<
•r*
)-H
e
o
S. 0)
>c u_
1
c
Ift *r-
3*07 C
C
w
?!
at
-M
SCOT
Condensa
c
0
(B Ctf 4J
-M +J 3
1- O
CJ co
2" Sf 2
" » t "1 1
i Ol en i
S ! ffl
£;|
U) : C
3 , «
(U t—
208
-------
TABLE -5'. 1-14. MAJOR ITEMS IN THE SCOT PROCESS*
Capital Cost Items
Operating Cost Items
Feed Heater
Fixed Bed Reactor
Waste Heat Boiler
Cooling Tower
Cooling Tower Pumps (2)
Cooling Tower Condenser
Amine Absorber
Amine Pumps (2)
Absorber Cooler
Stripper
Absorber/Stripper Heat Exchanger
Stripper Condenser
Reflux Drum
Reflux Pumps (2)
Stripper Reboiler
Lean Solution Pumps (2)
Piping . ,.-
Electrical .
Instrumentation and Controls
Site Preparation and Foundations
Painting
Fixed Capital Cost, $103 8,295
DIPA Makeup
4 gpd
Fuel Gas -.- ' .
1,970."CFM
Cooling Water
5,500 gpm
Electricity
1,650 kW ;
Manpower
% Man/day
Direct Annual Operating Cost, $1Q3
Maintenance 214
Operating Supplies 7
Labor 39
Electricity 1,375
TOTAL 1,635
* Design basis: 25,000 ACFM, 173 LTPSD sulfur recovered in the Glaus plant.
Source: SWEC estimates based on information provided by Pritchard Corp.,
September 14, 1981. : . -
209
-------
901 I '1S03 9NU?H3dO
lQ3Hlti
V)
CO
LU
U
§
Q.
O
o
to
!iso3
T3
O,
C
o
•p-
m
o
«-
c
c
o
•a
0)
U)
on
a
•a:
LU
co
3
£
CO
o
u_
o
o
u
uu
OS
210
-------
x\
1— ^UJ
£11
ij
o ^
2tn
"3
fS
i— cn
UJO
OS
Si
?
fc
go:
j Si
§=»
3
a.
aS
LuS
tuts
u.
>_
s —
Ul Z
OS *' '
,
X.
ft
ci
o
«
i^:
~ ,'.
3
cvi '
CVJ'
ci
**
s '
ci
S '
5 -= s
ej "^ **
0 0
1
Ci
a
^
ca
o
in
CO
*
CD
Cf
O
sf
U
t—
OD
s
ca
O3
•0
a?
o
—
CD
0
in
03
$
CO
i
o»
tn
t/i
1
o
211
-------
The MDEA process can also be used in the Glaus tail gas cleanup. Its
operation would be similar to the SCOT process, except the DIPA solution in
the. SCOT process would be replaced w.ith the MDEA solution.
Table 5.1-15 gives the composition of the TOSCO II retort gas before and
after MDEA treatment. The C3/C4 gases may be similarly treated.
Table 5.1-16 presents the capital and operating cost components of the MDEA
process as an acid gas removal technology as well as a tail gas treatment
technology. Specific cost curves for the two applications are presented in
Figure 5.1-13.
TABLE 5,1-15. RETORT GAS COMPOSITION BEFORE AND AFTER MDEA TREATMENT
Component
H2S
RSH
cos
H2
CO
C02
CH4
C2H4
C2Hg
C3H6
CsH.8
H20
TOTAL
MWt.
MWt
34
56
60
2
28
44
16
28
30
42
44
18
. Untreated
Gas
Ib/hr
12,197
14.5
120
3,590
8,380
79,070
52,510
34,383
19,958
1,324
652
932
213,130.5
Treated Gas
Mass
0.005
0.008
0.03
2.03
4.73
31.26
29.65
19.42
11.27
0.75
0.37
0.48
100.00
20.
Mole
0.003
0.003
0.01
20.82
3.47
14.59
38. 06
14.24
7.72
0,37
0.17
0.54
100.00
54
Mass Flow,
Ib/hr
8.8*
14.5
60
3,590
8,380
55,350
52,510
34,383
19,958
1,324
652
843
177,073.3
Flow,
Ib-moles/.hr
0.26
0.26
'• ' 1.0
: 1,795.0
; 299.3
^ 1,258.0
3,281.9
1,228.0
665.3
31.52
14.82
46.83
8,622.2
Total
Total
Total
Total
H
0
C
S
14,
25.
59.
o.
64
45
41
03
25
45
105
,930.
,059.
,192.
47.
6
1
9
8
* Assuming the after treatment concentration of 30 ppmv H2S.
Source: DRI estimates based on information provided by SWEC.
212
-------
TABLE 5.1-16. MAJOR ITEMS IN THE MDEA PROCESS
Acid Gas Removal3
Capital Cost Items
Absorbers (2)
1-7' diameter x 52'
L-3' diameter x 36'
Stripper
3' diameter x 30' ,
Flash Tank '
4,000 gal
Surge Tank
11,000 gal
Ami ne/ Aim'ne Heat Exchanger
24,700 ft2
Still Condenser
17,110 ft2
285-HP fan
Lean Amine Cooler
31,350 ft2
830-HP fan
Still Reboiler
24,810 ft2
Amine Reclaimer
2,480 ft2
Reflux Tank
2,150 gal
MDEA Pump
2,500 gpm @ 310 HP
Still Reflux Pump
10 HP
,
Piping
Electr-ical '
Operating Cost Items
MDEA Makeup
50 Ib/hr
150 psig Steam
22,140 Ib/hr
Electricity
1,075 kW
Manpower
2 Men/day
Direct Annual
Operating Cost, $103
Maintenance 480
Operating
Supplies 17
Labor 138
Steam 591
Electricity 255
TOTAL 1,481
Tail Gas Treatment
Capital. Cost Items
Absorber
9' diameter x 40'
Stripper
11.5' diameter x 50'
Flash Tanks (2)
6' diameter x is1
Surge Tanks. (2)
6.' diameter x 30'
Reflux Tank
2' diameter x 8'
MOEA Pump
1,360 gpm @ 125 HP
Reflux Pump
1,400 gpm @ 9 HP
Amine/Amine Heat Exchanger
16,000 ft2
Lean Amine Cooler
20,000 ft2
530-HP fan
Still Condenser
10,900 ft2
182- HP fan
. Still Reboiler
15,800 ft2
. Amine Reclaimer
1,600 ft2
Piping
Electrical
Operating Cost .Items
MOEA Makeup
0.7 Ib/hr
150 p'sig Steam
8,370 Ib/hr
Electricity
;3,190 kW
Manpower
2 Men/day
Direct Annual Operating
Cost, $103
Maintenance 244
Operating
i Supplies • 7
Labor 138
Steam 284
Electricity 149
TOTAL 822
,
1
'
:
, ' .
Instrumentation and
Controls
Site Preparation and
Foundations
Painting
Fixed Capital Cost, $103
19,000
Design basis: 2,500 gpm MDEA circulated.
Design basis: 1,360 gpra-MDEA circulated.
Source: SWEC.
Instrumentation and
Controls
Site Preparation and
Foundations
Painting
Fixed Capital Cost, $103
9,420
213
-------
9OI $ '1SOO 9N!I9a3dO 1WNNV 10381(3
p
f\i
ITS
\
\
\
\
\
\
\
\
8
m
ro
S
a.
=3
O
5
o a
IfJ ft
o
s
o
O t3
O
to
CO
UJ
o
§
a.
m
LU
LU
OS.
CO
o
-------
Total Sulfur Emisslons—•
The four major sources of sulfur emissions (as S02) from the TOSCO II
plant are: .;
• Ball heater/thermal oxidizer ... -
• Ball circulation system stack .
*• Tail gas from the Wellman-Lord unit
• Process heaters/furnaces and utility boilers.
The ball heater burns the treated fuel gas (135 ppmv H2S) and untreated
•shale oil, while the thermal oxidizer uses the C4 liquids and untreated shale
oil as the fuels. The major source of S02 in these systems is the shale oil,
as it contains approximately 0.9% sulfur by weight. The total S02 emissions
from these sources would be in excess of 1,100 Ib/hr; however, Colony claims
that about 95% of the S02 is absorbed on the raw shale, thus only 5% of the
S02 is emitted to the atmosphere (Colony Development Operation, 1977). The
ball circulation system emits the flue gas from the steam superheater which
also burns the crude shale oil. The tail gas from the Wellman-Lord process
contains approximately 105 "Ib/hr of S02 (at a sulfur removal efficiency of
92%}. All process, heaters and furnaces and the utility boilers consume the
treated fuel gas; therefore, they emit insignificant amounts of S02, with the
noted exception of the hydrogen unit furnaces. These furnaces consume a
large quantity of the fuel gas, hence emit a significant quantity of S02.
The fuel needs for various heating systems have been 'provided in
Tables 4.2-22 and 4.2-23. The total S02 emissions from the plant are
presented in Table 5.1-17.
5.1.3 Nitrogen Oxides Control
In oil shale processes, nitrogen enters the system from; two primary
sources: (1) the fuels derived from the raw shale, and (2) the;air required
for combustion in the various furnaces, heaters, auxiliary boilers and
incinerators. A portion of this nitrogen is converted into other forms such
as nitrogen oxides (NOx) and ammonia (NH3). The NOx produced during fossil
fuel combustion are emitted as NO and N02 in flue gases. These compounds are
formed from the oxidation of nitrogen compounds (e.g., ammonia, cyanides) in
the shale-derived fuels and/or from the fixation of atmospheric nitrogen
(N2). A large portion of ammonia resulting from the pyrolysis of the shale
is usually removed in the gas condensate, or foul water, when the retort gas
is cooled or scrubbed with water. This removal and subsequent recovery of
ammonia provide an indirect control over NOx emissions. Since the recovery
of ammonia from an aqueous solution also constitutes water pollution control,
this aspect. of the NOx control is discussed under water management (Sec-
tion 5.2). The portions of ammonia and fuel-based nitrogen that are riot
removed in the gas condensate may require removal or control prior to
emission to the environment. Federal and Colorado State standards and
regulations limit NOx emissions because of their potential role in the
formation of photochemical smog and acid precipitation.
215
-------
TABLE 5.1-17. TOTAL S02 EMISSIONS FROM THE PLANT
Stream
Number
18
19
57
91
104
118
119
125
138
179
TOTAL
S02 Emissions (Ib/hr)
Case: Studies
Emission Source
Raw Shale Preheat
System
Ball Circulation
System
Sulfur Plant
Hydrogen Furnace
Coker Feed Heater
Gas Oil Heater
Gas Oil Reboiler
Naphtha Heater
Diesel Equipment
Utility Boilers
Control Description
c
We 11 man- Lord
d
d
d
d
d
—
d
A,Ba ,
51.0
94.3
94.5
27.4 ;
2.8
0.9
3.8
0.4
20.0
7.2
302.3 •
Cb
44.7
94.3
—
23.9
2.4
0.8
3.3
0.3
20 . 0
6.3
196.0
The S02 emissions have been taken from Colony's PSD permit application.
The data are calculated. The emission from the preheat system has been
reduced by 95%, as claimed by Colony.
Amine is the primary control for the process fuel. Adsorption of S02 on
the raw shale serves as the secondary control. i
Amine Cor Stretford) is the primary control as the treated fuel gas is
used. . •
Source: DRI estimates based on Colony Development Operation, 1977.
216
-------
Inventory of Control Technologies— .
There are three categories of NOx control technologies: ' \
* Reduction of nitrogen in the fuel
* Combustion modifications ,
* Stack gas removal.
These processes are shown in Figure 5.1-14 and are discussed briefly in
Table 5.1-18.
Reduction of nitrogen in the fuel. Burning fuels low in nitrogen is the
simplest method of controlling NOx emissions arising from fuel-based nitro-
gen. Hydrotreatment of fuel oils and water scrubbing of fuel gases are
fairly effective in removing the fuel-based nitrogen.
Combustion modifications. . The generation of NOx by thermal fixation of
atmospheric nitrogen is dependent upon the flame temperature, concentration
of nitrogen, time history of individual combustion gas pockets, and the
amount of excess air present. To some extent, these variables ;are control-
lable, and the production of NOx can be minimized for a particular combustion
process.
Combustion control of NOx may be accomplished by several methods. One
approach is design and operation of burners with fuel-rich mixture ratios.
This technique, called off-stoichiometric combustion, produces low flame
temperatures and, hence, potentially Tow NOx formation. A significant excess
of oxygen is avoided in the combustion zone by diverting some portion of the
inlet air through, remote locations in the burner or through entirely separate
secondary combustion air ports. . , •
Another NOx reduction technique, based on combustion modification, takes
advantage of the strong temperature dependency of nitric oxide (NO) formation
on peak combustion temperatures. Reduced flame temperatures may be obtained
by direct reduction of gas temperature or by indirectly increasing heat
transfer. Direct techniques include recirculating product flue gases back
into the combustion zone where they serve as diluents absorbing heat, thereby
reducing maximum flame temperatures achieved. Other direct techniques are
reduced combustion air preheat and water/steam injection. The latter is more
applicable to gas turbines. Indirect NOx reduction relating to. the combus-
tion process usually involves furnace designs with increased burner spacing
and heat removal capability. Flame temperature reduction does not reduce NOx
formation from fuel nitrogen but does reduce atmospheric N2 fixation.
Stack gas removal. Flue gas treatment for NOx removal is a relatively
new, developing technology. Two broad categories may be defined: wet
processes in which NOx is absorbed into an aqueous solution, and dry
processes in which NOx is reduced by ammonia.
The wet NOx removal processes also serve as a mechanism to reduce sulfur
dioxide emissions and, as such, can provide effective environmental control
217
-------
NITROGEN OXIDES
CONTROL
TECHNOLOGIES
FUEL NITROGEN
REMOVAL
COMBUSTION
MODIFICATIONS
STACK GAS
REMOVAL
SOURCE'- SWEC
NH3
SCRUBBING
TWO-STAGE
COMBUSTION
LOW ^-EXCESS
AIR
FLUE GAS
REC1RCULATION
UDWER TEMPERATURE
THROUGH FASTER
HEAT RELEASE
ACTIVATED
CARBON
ABSORPTION
CATALYTIC
DECOMPOSITION
SELECTED
CATALYTIC
REDUCTION
THERMAL
DENOx
ELECTRON BEAM
SCRUBBING
ABSORPTION
REDUCTION
ABSORPTION
OXIDATION
OXIDATION
ABSORPTION
REDUCTION
FIGURE 5.1-14 NITROGEN OXIDES CONTROL TECHNOLOGIES
218
-------
V)
LU
M
0
X
IU
l—
o
o
0
VI
UJ
a
o
z
UJ
(U
o
as
Z
"
o
UJ
as
t-
s-
LU
S
S
1
A
3
m
i-
01
at
QJ
re
•4-»
T3
ctS.
Ul
O
Ul
a>
Ol
re
i
2
<
^
C
0)
B ui
§•3
> VI
a
a
(U
u
e
Q
£
f.
a>
Q.
at
"a.
o
e
Q.
g1
^
1
Q.
Si
Control
Technolo
c •
o ^'o S
T3 C >,
4) OT.O X •
eu <*- X C
U '^- (0 C
01 4- O
•P e c T-
o o •— cu -P
ui E O- 3
o "i J= £ o
a 3 *j c o
•£
.O Ul
01
X
' X Z
st!
o ~a
o
at S-
t ?"
O CQ
Ul
TJ
cu^d 8
III
01 O S-
as 4- a.
' C
o
a.
^
(0
o
S.
01
o
*-* ,
>i aT
"i"0 **
"STJSs5 .
ui o> o to
•M o c a. a
^iiis
i •
s. s-
II
u 5
ja "3 -
n en
54=
^
"Sf
I"
4J -P VI
CLC Z
-JO* S
> .2 3 <
g
C Ul
(U O
a. u
x _
c *«
•r- -4J
o
VI 4->
o
i*1
4-> C
v) O
U) -M
(0
at at
3 C
CQ ••-
>v
i. 1 —
a> to
••— u
o s.
T3 S
C 0 -
(O, U (U
ui ui .a
t- C (0
cy aii—
i. Ul (O
3 CU >
CQ -o m
X
1 ^
PI
-III
1||.2
§11-5
i. . •
oll-sl
3: +j u c 3
4n> Ul O ^
3 O)-r- m
C.J2 C +J O
U **•* - T3
«c N o ** m
X
ti o t -a c
CU 0 •— 0 3 J= UJ CO C 3
t J3 4-» Ul C •«- J3
§ 0 *3 *S 3 C* 0
3
O "V.
cu a. o
i- U
».- 5.
Ul 4J Ul
S. O) O
s- qj to -^
oj a. cu ui
r- O S- Ul
.^ U f-
o o _c e
o
(0
s-
a.
o
^
0
Ul .
-f-
r— CU 4— •
0* -^ X
S- 3 CO
-P -P cnz
O t- U) <*- '
U CU O
.^ § "" o
•»-» Wl •»-
*3 S f— U
t~ <5 33
O) - ui C
U -P 3 -r-
£• C
•*- CU -^ Ul CO
U C -f S.
S- N S- S- 4-J
3 CU >O
ui C — 1 (O U, OS V)
U C •
c<3 OUT
<*- 0 0>01
0 VI 3 i-
r>v -f-
C • . "O Q. •
0 ^- C i
F- CU fl3 *i -
•P 3 Ul Ol •
Q.4- Ul >» .C +J
3 "O ' -P (0 C O
Ul C (0 -P O U
C (O r— ft) Ul
O 3 U -r- P-
U C U O (0
Ol S- S- 3 -O Q,
x u a. cj m u
O ui «
VI CU 3T
Sz
O P 4-
cO O
1— fc.
Ol 3
Ul C Ul •
3 -P- C •
O -P O ,
c - t. y i
re x
•5 C ,0 C .
vi re — i co
1
i-H
CU • C
i i s a - « ' i
)-4 -r- to ui re -i—
+J CU •«-> CU U O (0
>iC3 U1U) V)U1CM>
3 o TJ c ui i re
3i u • o i — at i — "
UlC'P U1(O U ft! C ui
§-r- O Ul i- 3 O -r- Q CU
"O T- O (O-P S- U -i- V>
-U CJ O.CL Q. t- -P U)
4^4^re cu cutocu*
•r- c s- -C >u s- e t- u or
ffocuoi sc 3scuor-
i— Q.-r» .O O O Q. i- ^
V5 Q. Q iT OS U Lt.UOQ.re
"re
g 1
Ul Ul Ul ,
re • o ui 3 -P
^^ -C CU O Ul
O i- — z i- re re
<*- *— , ^ t— cn o
0 T3 . -r- r— C
C P > CU •>-/ Ul S-
o re re u 3 re
•P -f— re "o ui s. cu
s. u re i. i— 1-7 i-
ui X -P "s O
Sc o o re •*- t.
o z z u ui a.
c-
o
c *>
4-1 •*•* -P O *f~ -P *r~
••— xio re'o cure3as
•P&-U1 -P U r— .*•> T3 (_J
u re 13 recu cprecuvi
-------
CA
CU
O)
3
.C
IQ
>
-a
' (0
•r*
O
Ul
•33
S ^
0
«
£
&. •
CU
a.
Of
a.
u
c
a.
g1
(0
S.
a-
r— |2
Contro
Techno
•s
if
3 +3
E f. •
O
S s
oj S
i — i
3* TJ
•0 >
U
Ul S-
c eu
1 1
' t
"(0
O
OJ
*•
X
§
s
a.
O 0)
•-T 3 o' .
ca M
(0 C 1C
"S !*
O CU UJ
0 '— CS
to. . c
•+J - 4^ 01
3 S. in T-
u> O O O (J
C «J (J —
O •*•» (0 H-
O C fc. r- *.
J_ >_ r» *3
O *l- (J rtJ T"
- Ct, O (0 U -C
O
4-
O
(0
2
3
O
C
« x
ll
cu
O)
[0
Ul
r2
Q.
0 >,
CL. O
CM
S
^
cn
w
X
i
CO *-
(0
O >
s-l
^
x +* . ^
«'^ i^
e • *5
rtJ S u x
•r- 4-* CI) 3 O
0 U U> T3 Z
« U O.CU Z
E
0)
ca
01
0 5
s- ja
U 3
cu s-
EiJ
0)
0^
> (0 C .
•r- •— C0
Ul
c w «
ty « 3;
(0 U ui
tfl "T"
2 «-.ti .
3 3 C O*
a*«— m w
S-
3
i.
C
>
4-9 f—
Ul r—
e ro
11
0 0
z u
c?
UJ
n
cn
C M+J
sll^
Ul s u. u
c
0 C
•»- o
£"0
0 3
Ul "O
'C
4-» a
3 10
ui £.
c cu
Q C
(J CU
o cy
£
Ul
3
O
1 X
+J O .
*3
CO (0
•a
CU
O -r-
~° S
O O
z u
'**
3
m
>
(0
•S
O
ey
c s- .
•r- <0 «
TJ T3 S
CO C W
q i« ^i?
S.
S§1
•S-10
ill
CM V O
4/1 S TJ
o ^ 'x
z m o
c
o c
Q.4J
Ul •>—
-Q X
(0 • C S CU
"O , E •»• v
r— S- O S- Ul *f £-
f •*-> t. O *f- X ell
CJ Ul Q. *»- TJ O >
o
o
rtJ
o
£•
£
Ul
3
O
(0 X
t/1 10
TJ
rd
Ul r—
• C (0
s u
•w g
"o o
Z 0
M
o
33 X
cn z
-^«
xo •
o vi m
(0
o > o
:D i_ s_
o
"S
U)
3
2
(0
0*0*
o
a121
at
I'-S
S'i
c •
c o c
*> I^J J-*
(0 i. y
TJ O 3
•r- U» TJ
X -fl CO ,
CO
1 —
CTl
1— 1
a>-
o
u
o
Ul
cu
£
o
(0
£.
o
(0
3
s
1
(0
ca
1
o
*+J
<0
o
>£
c
c
o
TJ
Ul
-Q
u
IU
Source;
220
-------
TABLE 5.1-19, TOTAL NOx EMISSIONS FROM THE PLANT
Stream
Number
10
18 .
19
91
104
118
119
125
138
179
TOTAL
Emission Source
Mine Vent
Raw Shale Preheat System
Ball Circulation System
Hydrogen Furnace
Coker Feed Heater
Gas Oil Heater
Gas Oil Reboiler
Naphtha Heater
Diesel Equipment
Utility Boilers
NO>]C Emissions
:(lb/hr)
, 250.0
1,314.8
' . ". 113.4 .
: 82.2
; 8.4
2.7
; 11.2
1.3
' 267.9*
'• 21.6
2,073.5
Source: Colony Development Operation, 1977, except the quantity :noted with
an asterisk (*) was estimated by SWEC.
in government regulations restricting their emission. Federal and State
regulations limit these hydrocarbon emissions because of their role in the
formation of photochemical smog and ozone production.
Inventory of Control Technologies—
As illustrated in Figure 5.1-15 and discussed in Table 5.1-20, hydro-
carbon emissions can be controlled by .the following categories of control
technologies: : ' •
• Additional sealing of process equipment
• Vapor recovery
* Complete fuel combustion
• Catalytic converters ;
• Thermal oxidizers. •
-. ' , ' • • !
222
-------
HYDROCARBON
CONTROL
TECHNOLOGIES
ADDITIONAL SEALING
ON PROCESS
EQUIPMENT
VAPOR
RECOVERY
COMPLETE FUEL
COMBUSTION
CATALYTIC
CONVERTERS
THERMAL
OX10IZERS
SOURCE: SWEC
FIGURE 5.1-15 HYDROCARBON CONTROL TECHNOLOGIES
223
-------
V)
s
1
i
h- •
—4
O
H-
Z
U
Z
o
s
s
s
>-
•x.
u_
o
V)
OS
1
LU
U.
LU
?
H*
•p
c
m
f
V)
0)
Performanc
Operating Principle .
^
O)
o
'o'o
t. c
•p f
c u
O 4)
CJ t—
i/>
U) P f—
_ o c o
•O (. 4) U •
at — € P -P
•P 3 -P C C
c cr w o rg •
4i at at u t—
. s -P as > Q,
*r ^ >(" 5 ?
a* O. C ^ *^
•i- O "S *
0.3 a-J-o,
o -a c -P > •»-
C nj at
r~ tlj .C O Ul -Q
/— *»' *J C
§-P OS
vi at a> .a o
Ul O S- 3 S. S_
U O T3 eO'«(-
Ol +J O T3
W C >• V> t. 4J
4» ••- *— O T3 -P
s- -p .a u >» c
•»- Hi (0 -CO)
3 E- & VI > .
a* at o ••- 4t 41
4) O. 1- jC -C S-
Q£ O O.-P 4J Q,
c
i»
o
a.
(^*
la
2 *.
i '
u
c c
5f *
u nj ja
3 U -i- <*-
T3 O 01 O
m u» at
1 >
&^ f- Ol .«»
lo*5)£S'o
•P 3 U> S.
3 <+- 01 ^ +J
a i- +^ e
< o ai 3 u
Double seals on pumps and
rotating machinery and caps
on open-ended valves reduce
hydrocarbon losses from the
equipment.
•— c
(0 O -P
c c
O O) « 4)
-p- C w> S
*i T- 4* Q.
._ ^- U .p.
•O itO O 3
•O 41 fi. O"
<: v> CL LU
§'
S &• Wl
Ili
O -P
"CT £
^ § •?
13 S £•
at i- at
e a1 a»
m at .c
CJ S- -P
W)
5
(O
wi 4)
n) v
J=-r- W
U -P
-C 4t O
O VI
P 0 S
« P 4)
w -a at
41. U
at •*•> i-
2*0.0
«j a. tn
•i- as
41 -
S -a
O "O 3 TJ Wl
.5 >* w c >»
< -C 3 ,
4)
>
O
(J
OS
.a
a.
.>
"O
at
c
,— «j
U
•i-
S
at
•P -P
(Q V)
1.2
P
8
4-
O
t- o c
-P VI
•o c s-
41 4) 4)
at s >
C Ck C
-i— O
at 3 u
£2 cr
•P 41 JJ
ai if
•P at at
SS» ^i .
•P at O
*r s *ti >
t/l 4t
rtj > -o
•P *r- at
(0 W O
u c m
H- ai t.
ns -P -r-
to c
r— *~ •?—
4) 4-* E
« +* ^
«P O W
c* vi at
as -P o
. S. C
2 Q.C
3 OJ-P
cr c c
t. > (H
O 4)
c o c
U1 -P
4) U) 3
o m o
a ^ t.
,_:
S
•
Q.
r^*
"ra
u
4)
e
1
• «
c o^ en ^o
c vi "O t. en v>
O O (O C 3 VI
•p .a en t x -P £. u> o
> A at at at -i-
e w> .c vi 01
o a» «™ s -P u» ^
y j= at «3 O 4) 4)
•P 01 4) U >
C 4> i. !« O C
OJ <*- -r- *J O S. O
U O T3 VI 4- Q. U
£.
> 4> -P U) 91
Hot exhaust gas is passed o
a catalyst where the unburn
hydrocarbons are reacted wi
the excess air in the exhau
gas and are converted to CO
and H20.
U)
U S.
41
c cr c
«3 £ 1
C V)
O S- (0
*** 4) Q)
•P -C
(tt -P 4)
TJ O .C
X >»
O C C
(Q •*!—
at
P T3 v>
Of C P
t
E. i— u)
*o o c c
O r-( i- flj
cn Q
Waste gas streams containin
unburned hydrocarbons are
burned with excess air and
additional fuel if needed t
completely oxidize all
hydrocarbons to C02 and H20
(A
s_
i— 4)
*- "O
41 'f
jr x
1=0 '
]
ra
r-«
C
p
«p
m
u
o
VI
o>
«s
e
• o
m
LU
I
•g
• j-
at
ed on. information front Rese<
VI
m
.a
LU
- 3'
••
3
co
224
-------
Additional sealing of process equipment. Hydrocarbon emission control
by. additional sealing of process and storage equipment is best accomplished
by engineering these features into the plant. This includes double seals on
tanks, pumps, and other rotating machinery, closed-loop sampling, caps on
open-ended valves, and periodic monitoring of equipment to find hydrocarbon
lea.ks quickly./ This will result in a minimum additional plant; capital cost
and; will more than pay for itself due to the value of the hydrocarbons which
are prevented from being emitted.
Vapor recovery. When hydrocarbon vapor emissions cannot be controlled
by additional sealing of equipment, a vapor recovery system canibe installed
to collect and condense the vapors by refrigeration and return them to the
process. :
Complete fuel combustion. The most cost-effective way to control
hydrocarbon emissions from fuel combustion processes is to operate the
process with enough excess air to ensure complete oxidation of all hydro-
carbons to C02 and H2Q, i.e., complete fuel combustion.
Catalytic converters. When complete fuel combustion does not occur, the
hot exhaust gas from the process can be sent through a catalytic converter.
In the catalytic converter, the gas is passed over a catalyst where the
unburned hydrocarbons are reacted with the excess air in the exhaust gas and
are converted to C02 and H20.
Thermal oxidizers. Hydrocarbon vapor streams or any other waste gas
stream containing unburned hydrocarbons can be burned in a thermal oxidizer
with excess air and additional fuel, if needed; this completely oxidizes all
hydrocarbons to C02 and H20.
Hydrocarbon Control Technologies Analyzed— '
The hydrocarbon emissions in the TOSCO II plant emanate from the leakage
in the valves, pumps, etc., as the fugitive emissions from oil product
storage, and due to the incomplete combustion of the fuels.
A thermal oxidizer system was examined for controlling the hydrocarbon
vapors generated in the lift pipes in order to reduce the emissions from the
preheat system. The oxidizer system burns additional fuel in order to
incinerate hydrocarbons picked up by the hot flue gas during preheating of
the fine, raw shale. This system has been proposed by Colony (Colony
Development Operation, 1977).
Hydrocarbon emissions from diesel-burning equipment are controlled by
installation of catalytic conversion systems. The least costly fugitive
hydrocarbon emissions control for storage tanks is proper sealing. Alter-
natively, vapor recovery can be used, but the expense is extremely high
for these systems. As a standard industry practice, double-sealed, floating
roof storage tanks are provided for volatile product storage. Internal plant
leaks are controlled by use of adequate seals and strict maintenance proce-
dures. The furnace and boiler stacks emit partially burned hydrocarbons.
225
-------
Except for using proper combustion practices, no other technologies are
provided for controlling hydrocarbons from the fuel combustion sources.
Table 5.1-21 lists the design parameters for the thermal oxidizer, while
Table 5.1-22 lists other hydrocarbon control practices arid equipment
considered. Table 5.1-23 presents the costs for hydrocarbon control for the
entire plant. A cost curve for the thermal oxidizer is presented in
Figure 5.1-16. ;
TABLE 5.1-21. MAJOR ITEMS IN THE THERMAL OXIDIZER*:
Capital Cost Items Operating Cost Items
Oxidizer with Brick Liner . Fuel
pip1ng • 610 x MMJtu/hr
Electrical Maintenance' •
Instrumentation and Controls
Supports
Painting
* Design basis: 2,080,200 ACFM.
Source: SWEC.
1 ' , ' " • ' " ' ','
TABLE 5.1-22. HYDROCARBON CONTROL PRACTICES AND EQUIPMENT
Capital Cost Items Operating Cost Items
Floating Roof Storage Tanks . Maintenance
1-150' diameter x 40', 150,000 bbl
2 - 140' diameter x 40', 219,000 bbl total
Welded API 650 code
Double seals
Carbon steel
Complete Combustion of Fuels
Dual Mechanical Seals on Pumps and Valves ;
Catalytic Converters on all Diesel Equipment !
Monitoring Equipment ;
Source: SWEC.
226 . :
-------
^J
g
s
z
o
1— I
5 -
I
0
a.
^E"
o
ca
•^
8.
ae
a
>•
Z
U.
o
^
o
o
eo
i
f™*3
in
UJ
2
IB
O in
s. -
+•> O
C 0
•— o o
O r-
t- 10 4->
3 V)
e o
•e u
§'
4-) in
s. o
r— 0) O
10 0,0
*> o <«•
0 >-<
i— i—
IO +J
3 in
c o
«^
T '**"»
•ticb
d.0
IO O
at •«->
X in
•i- O
U. 0
in
S- -P
Ol -r-
.Q C
s =>
•z <+-
o
c
o
•1—
18
1
. ,_
o
s.
1
c
o
+3
a.
tL
u
in
..&
r~»
o
i.
c
o
S S-
10 01
»
-u
10
01
01
°r
01
"(3
to
1
U)
4)
Nl
•5
i
,_•.
as-
g
01
1—
CO
r-(
in
CO
o
s
1
1
.J_)
g
g^^
*3
o-
UJ
"a!
(n
o>
5
u>
s_
Ol
*j
.i.
• ID •!-
C
><=)
i.
01 O)
> e
O *'••
U -i->
Ol IO
^£ 0)
S.
W3 H1
(O
C9
10
S
s-
5
1—
T3
C
10
SL
Ol 01
i. N
<0 -i-
•— "O
U. -r-
X
* o
0
CO
CM
^2
,^4^
<*• CO
IO CM
~
'
A .a
i-t in
^> CO
o
go
in
CO
i
i
y
0)
&
to in
5 3
u) a,
t S
I 1
a, , >
ai
01
(0
s.
5
to
I6*>
O 01
a: o
en 10
c « c
•*" &!• 0}
+j e 4->
o (2 .5
r- (0
U. •£.
1 1
1 1
Iin
0
%
CM
5^
CM
-
iH
.O
CO
««•
CM
f^
1—
0
1—
'
-p
in
o
u
i«—
o
S-
c
o
u
10
3'
C
to
P*,
pw
IO
+J
01
. "D
S.
o
1*-
c
o
(J
ai
a>
a>
18
10
3
C
c
IO
ot
+*
i.
11-
in
O)
IO O
u
1. CM
01 CO
0.09-
O
•o 1o
c
•si
+->
Q. Ol"
10 U
u c
IO
r— C
3 S
C C
10 10
f..
IO £
•P O
0 1-
•P H-
ai o
J= 0
-P 0
oio"
C CO
u -a
IO C
S- 10
^ in
in c
u-3-
0)
£ &
IO IO
S3-'
1*- UJ
ll
IB
ie o
u &•
•" «-
•o
c o
•I- O
o
CM
"-XI-H
U) '
0)
c -5
^
J3
i
0
LU
l/>
^^
-o
01
-o
^
2
Q,
C
o
+3.
10
i.
£
c
c
o
0)
U)
10
in
01
18
•J
in
01
a:
Q
. .
01
u
3
O
l/l
227
-------
gOl % 'ISOO 9Nll7U3dO 1VDNNV 1D38IQ
ITS
o
t«-S
to
O
cvj
\
\
\
n
o
_i
O£
LU
u_
o
CVJ
10
c
o
•a
-------
, Total Hydrocarbon Emissions'—
Table 5.1-24 summarizes the hydrocarbon emission sources ! and control
equipment used for the emissions.
TABLE 5.1-24. TOTAL HYDROCARBON EMISSIONS FROM THE PLANT
Stream
Number
Emission Source
Control Description
Hydrocarbon
Emissions (Ib/hr)
10 Mine Vent
18 Raw Shale Preheat
System
19 Ball Circulation
System
91 Hydrogen Furnace
104 Coker Feed Heater
118 Gas Oil Heater
119 Gas Oil Reboiler
125 Naphtha Heater
138 . Diesel Equipment.
179 Utility Boilers
"Product Storage
Valves, Pumps, etc.
. TOTAL .
Thermal Oxidizer
Catalytic Converters
Floating Roof Storage
. Tanks
Maintenance
50.0
270.0
; 0.3
0.2
: 0.1
'. 0.1
7.7*
0.4
24.4*
Source: Colony Development Operation, 1977, except those quantities noted
with an asterisk (*) were estimated by SWEC.
.5.1.5 Carbon Monoxide Control
Carbon monoxide (CO) is usually formed by incomplete combustion of
fossil fuels. Normally, an excess of oxygen is supplied to a combustion
process to ensure that all of the carbon in the fuel is converted to carbon
dioxide (COa)- When a shortage of oxygen occurs in the combustion process,
some of the carbon is only partially oxidized to CO. Federal and State
standards and regulations limit CO emissions because of their' deleterious
effect on the human respiratory system.
229
-------
The easiest and most cost-effective way to control CO emissions is to
use excess oxygen in the cpmbustion processes to ensure complete combustion.
When incomplete combustion does occur, catalytic converters or thermal or
chemical oxidizers may be used to oxidize the remaining CO to CQ^.
Inventory of Control Technologies—
Figure 5.1-17 shows a list of the applicable carbon monoxide control
technologies, and Table 5.1-25 describes in detail the features of these
control methods.
Complete fuel combustion controls CO emissions by not allowing them to
be formed. This is done by operating with enough excess air to ensure
complete oxidation of all carbon to C02 instead of only partial oxidation to
CO. When CO is formed in a combustion process, a catalytic 'converter or
thermal or chemical oxidizer can be used. ;
Carbon Monoxide Control Technologies Analyzed— ;
Diesel equipment will be used in mining activities, processed shale
handling, and transportation systems at the TOSCO II facility. The CO
emissions from these sources are controlled by using catalytic converters on
all diesel engines. Since the catalytic converters also control hydrocarbon
emissions, they have been included under hydrocarbon emission control.
Process fuels are burned in the thermal oxidizer, ball circulation
system, and process heaters/furnaces and utility boilers. The ;CO emissions
from these sources are controlled by operating the units with 20 to 25%
excess air to ensure complete oxidation of all carbon to C02. This is a
standard combustion practice, so no additional equipment or cost is associ-
ated with it. ! . .
Total Carbon Monoxide Emissions—
Table 5.1-26 summarizes the carbon monoxide emission sources and control
equipment used for the emissions.
5.1.6 Control of Other Criteria Pollutants
• . i
In addition to the primary air pollutants discussed so far, there may be
other criteria pollutants, such as lead, mercury, beryllium and fluorides,
emitted from the TOSCO II facility. Some of these pollutants are nonvola-
tile; therefore, they may be released only as fugitive dust constituents.
Any control of the dust will also serve to control the nonvolatile pollut-
ants. Volatile pollutants may potentially be released with the stack gases.
Some pollutants do not occur naturally and some are unlikely to form during
oil shale processing.
5.1,7 Control of Noncriteria Air Pollutants
Meaningful test data are not available to determine whether emissions of
noncriteria air pollutants are a concern. Consequently, no information on
. • • 230
-------
CARBON MONOXIDE
CONTROL
TECHNOLOGIES
COMPLETE FUEL
COMBUSTION
CATALYTIC
CONVERTERS
THERMAL
OXIOIZERS
CHEMICAL
OXIOIZERS
SOURCE • SWEC
FIGURE 5.1-17 CARBON MONOXiOE CONTROL TECHNOLOGIES
231 '
-------
LLJ
1
H
CJ
-J
§
5
0
U
LU
Q
^
§
E
S
5
u.
o
v*
01
s
LU
UJ
a^
?
*"?
iA
UJ
1
i—
(A
3
C
ffl
•3
(Q
U)
O
Ul
01
S
C;
m
4J
c
at
0. 3
O -«•>
> V?
at
o
4)
S
'• I
£
^
4)
°-
Operating Principle
_
O3
r— .2
o o
i- c
s-g.
O 41
CJ f—
•S'.'
C
«5
3 C
(Q 01
41
+J 4-»
= |
7 S
CJ
T3 O
(0 -r-
52
8
"*.
0
i- 0 C
O 4-» O
-tJ Ul
T3 C S.
41 S >
' C 0, C
.F- O
4> 3 U
-*-» 4) 41
ui S *>
m s. +j .
]s e*o.S
^- o o o
UJ T3 U -U
c
41
O
a.
^
aj
U
S.
i
0
°
sf
a> o
u> -a •
O s— en
TJ 38
C <&• Qj
o o a
u <*-
•So 5
U r-4 4J
13
4)
<-> O
(O CJ
£•>
Combustion process is ope
with excess air to ensure
complete oxidation of all
carbon to C02, instead of
only partial oxidation to
O)
3
„, °
0) 'r»
•M .(J
01 It
<— 3
ti
33
Ul .
j. ^
u at . -a.
r— 4)
+j *(— ai
4tl Ut U
U C 03
41 a.'a.
•
!LJ
m c
4^ 4J S
Ul -r-
C* Ul 41
fl tf c
4) ffl (0
_*- a c
or ™ c
(tj
O B
o S at-
Ul *J
• 4> Ul 3
C
4)
1
CL .
>*
ro
,'u
i
1
°
S. ,
o at
Sin O C (A
4) cj ••- o a
•f- d 4J O.
^ _C ^ J3 3i-
i. c
a* o o» at w o
> CJ 3 41 -i-
O r; 3 *- 4) 4>
(TJ H- X -M t- O
0 0 ffl O Q.U
i. at ui
4) A Ul Ul
a» *~ ' m
O.JJ 01
(A 4J -«J *J
•F- >^> U) ' • '
a> 2 3 «
u» t- ta o
« « -a -c u
O),C 01 X
3 *> 4) 0
4J U 4J
ui -H* , s, +j ai
J=^ 4J
X flJ Ul C S-
«u--g
4J 0 Jg ^. C
a; as 01 S u
u s.
S 4^
-51
(0 O
41
11.
C u) 0)
C 3
-C Ol
(TJ C (U
«15'
> W
(TJ S- i—
^ *3 4J
Jll
= "S.
.2 Ss
+J (TJ (O
3 4-»
x at ui
0 — S.
t O)
r— 01
ill5
4> O O
3 C 4-*
SO O C
*»^- 0)
at 4.* c
3 O O U
c
41
1
a.
>>
eO
o
£
S
0
^
^
B
O Ul
rH BJ
s|
CO
•fi."^ "
gS 3
U ^ nj
«J •*. 4J
CJ O «
s. -a
fi'5-SS
Waste gas streams contain
CO are burned with excess
and additional fuel if ne<
to completely oxidize alt
to C02.
Ul
OJ 2
JC X
j— -O
(+_ y)
O r—
at u
ai "-
t. Ul
3 4)
O" Q.
41 5?
C£ 4)
'
3
O
•f* 0)
3 J=
U 3
O •*-> .
•M ftj S
°^i
O 4->
4* -U Ul
•*•* r» Ul
oi nj
Ul 3 O)
at •*-
M 0)
X ui C
O 3 41
C
41
£
CL
^
nj -
"^
5^
41
O
CJ
°S
II ^
CO
|ss
y »— «j
c ® ^
CJ O ui
£
(Q ui
i ni
Gas streams containing CO
scrubbed with a solution
containing a chemical oxi-
dizing agent which oxidizi
the CO to C02.
Ul
f— S.
§2
55
O
00
s
c
o
J_l
i Associal
J
*j
1
s
•a
10
£
£
A}
0>
I
4-1
|
1=
O
•o
41
(O
J3
CJ
, 3
(/>
t-
5
232
-------
TABLE 5.1-26. TOTAL CO EMISSIONS FROM THE PLANT
Stream
Number
10
18
19
91
104
118
119
125
138
179
' TOTAL
Emission Source Control Description
Mine Vent . —
Raw Shale Preheat —
System
Ball Circulation
System
Hydrogen Furnace —
Coker Feed Heater
Gas Oil Heater
Gas Oil Recoil er
Naphtha Heater
Diesel Equipment Catalytic Converters
Utility Boilers _-
CO Emissions
; (Tb/hr)
440.0
43. 9
2.8
9.9
; 1.0
0.4
. 1.4
0.2
23.0*
2.6
525.2
Source: Colony Development Operation, 1977, except the quantity noted with
: an asterisk (*) was estimated by SWEC.
control technologies for such pollutants was generated for this manual.
Mention of species such as POMs (U.S. EPA, 1980) and trace elements such as
arsenic (Fox, Mason and Duvall, 1979; Girvin, Hadeishi and Foxj, June 1980)
are noted.
5.2, WATER MANAGEMENT AND POLLUTION CONTROL
As in other industries and oil shale operations, the TOSCO II plant—
from mining activities to final product and waste disposition—will produce
water effluents which will require proper disposal. These effluents may
contain the following pollutants:
•• Suspended Matter, Oil and Grease
• Dissolved Gases and Volatiles
• .Dissolved Inorganics .
• Dissolved Organics.
233
-------
This section describes the current, commercially available alternate
systems for controlling the above pollutants. The following, subsections
provide inventories of control technologies for each of the pollutant
classes, a discussion of advantages and disadvantages, and important points
to consider in selecting a particular technology. The performance, design,
and cost data for the leading technologies are also presented.
5.2.1 Suspended Matter, Oil and Grease ;
Undissolved matter found in wastewater effluents includes solid parti-
cles as well as oils and greases. The solids are usually the raw and pro-
cessed shale particles that are washed into the retort water and those that
are entrained in the retort vapors and subsequently removed in the gas con-
densates. The retort water and gas condensate also contain trapped oil and
oil-in-water emulsions. Service and storm runoffs contain suspended matter,
as well as oils and greases. Also, the source water contains suspended soil
particles and debris.
. In general, the control of suspended matter at oil shale plants will be
accomplished using conventional technology. For example, clarification in
gravity settlers (with addition of flocculants) and multimedia filtration
will, in most cases, provide adequate control. Associated energy consumption
and costs are generally low.
The control of undissolved oils and greases in oil shale wastewaters has
not been studied in detail. API-type gravity settlers have the potential to
provide adequate control for most of the waste streams generated. It is
possible, however, that some wastewaters will contain oil-in-water emulsions;
if so, additional control steps may be required. Heating the water or adding
chemicals may be sufficient to break the emulsion; otherwise, filter
coalescence (or possibly ultrafiltration) may be required. :
The degree to which emulsified oil'needs removal is dependent on down-
stream processing and reuse. In cooling towers, the oil may foul heat
exchange surfaces and thus require prior removal. Similarly, fouling, and
possibly foaming, may occur when stripping the retort water or gas conden-
sate. The extent to which such problems will arise is not known.
The energy consumption and cost of oil separation by gravity means are
generally low. Thermal or chemical treatment, if required, would cause some
increase in costs. Filter coalescence and, in particular, ultrafiltration
generally are more costly and would be considered only if other procedures
prove inadequate. .
Inventory of Control Technologies-'-
_ . .- - • , \
Figure 5.2-1 shows different types of technologies that apply to control
of suspended matter and oils and greases. Key features of these technologies
are provided in Table 5.2-1. :
234
-------
SUSPENDED i
MATTER, OIL 8
GREASE CONTROL
TECHNOLOGIES
GRAVITY
SEPARATION
CENTRIFUGATION
PHYSICAL/
CHEMICAL
FILTRATION
API-TYPE
SEPARATORS
•SEDIMENTATION
FLOTATION
COAGULATION-
FLOCCULATION
• CHEMICAL SEPARATION
.THICKENING
•SOLIDS FILTRATION
•FILTER COALESCENCE
• ULTRAFILTRATION
SOURCE' WPA
FIGURE 5-2-1 SUSPENDED MATTER, OIL AND GREASE CONTROL TECHNOLOGIES
235
-------
Uj
O£
C9
O
trt
0 .
as
I
S
UJ
Q.
to
5?
OS
o
U_
V)
UJ
*— »
C3
3
3=
CJ
1
trt
1
Uo
>• "
s
t-i
~
in
Ul
1
(A
C
O
CJ
tA
•P U)
U 0)
3 -P
"O Ul
CQ CO
UV tA
'11
•»- 4-
•O 3 .U
Ol CT wl
01 O 0)
u. a: o:
&
<— 41
Id •*-
0 •"
ly ^j
Components
Removed
01
a.'
u
c
£
Operating P
1*
2S
£•5
32
Ul
O u>
U> I—
,- 0
3 *f"
e *>
01 I.
0 °"
c
3 S->
Ul £.
3 01
jj *
**
Ul
O>
. J
tA
U)
•i- O
O M
•Q
«*- u
C
S 0)
111
•— -P 3
E u) -p
V- S-
O O -
<«- C
r- O
(O <— f-
§u m c
•*• 4«» o
0) O 1—
T, .2,2
01 *r» jQ .
C Wl U XJ
O *O " V> *P»
3 *o fa m •*-
S -otf
c uJ a> a» '
«U 0 +J-Of--- <0 Q.*f" E 'r* O
tn So S (O W *r~
-P >4>«U(JJ3^« S. (TJ
(0 -w +J a* *— nj +J
3 +J % S J3 C3. O
o* c s O) «u m f3 JQ a) i—
•oc-a^ns O ja *" "
Q O) O 3 u» -P £»
tO*DO Q) 0> t- U> -i—
>+- 4J c -u e u u •»- -r- (0
o^Saj**^10?"?
•t- c 01 -4J s. o> a»-t- o *—
to -r- (0V >U>4-»O
a. -P (0 uijztu-P o 3 s^ '
c
o
'"" . .
Q> *l—
*»•»-•*- (O tj O
C
> S- -T3 CU O
f- «J 0 S T3 rr-
«i a, fe. o -P
C ^ O W) 4^ O.I—
at *J >*-. a) «j ci o
•^ O) £- tA *i">
S- (« d 3 CL to J_
0 L. Ul ^- (U 0 CO
£ as 3 wi y> «*- a,
o
Ul
>
o
CO
<
o
.a
< <*- t- IA
c
•$'
(O
01
CJ
U)
£ •
Q. « «
0> U) -r-
-P O
£•«.§
a> to s-
11s
c
o
S-p'lo
•i- S.
dl > (0
S fO (i
fO £. (U
« W ui
4) tO «—
1113
t- 01 (0 tr-
•0 o u to
•i- U U
2 O (U
<*- f— S.
< o i- ra
M— .C
O Ul -P >
"— 3: O)
03 U) -P-
> ^a S.
, S. U
o i c u>*t?
a. s. <*- "o a.-
^j C
•P Ul 3 «t—
§u> ui c re
»— o s.
£- 4>T- U (TJ
tt5 ° c S-
O *^ TJ -r- tA •
4J C
<*- to TS >»
ui O
a> u co to
OJ C +J >» S-
co « ^- a» *
U -f— Wl
«- tA Ul (0 CO U)
o a -a t. a*
r^ ••— 01 JS CJ
0) fO r— C -P O
01 0 0 CD — t-
=> U U) C3 3 O.
(0
£
« c c*
.C 0 0 -^
CJ *i- «i— ' CO)
3p- r— *tO +J C
3 3 U (0 0>
f at u •*- c- jd
u> to U g (0 O
1-32S&S
Q. s^* U_ CJ CO f—
,J2
*— (O ^3 •— S
•r- Ul CO O OJ
Ul
^P "^Z
CTi U
Cl 'f
o °"
a
C 03 -D
O C tU tA
o."o .- 4-> 01 U
U* '^- +J
U> 3 •— S. CT
*0 Ul -*f- O C
"..'"••oS
Ul CU Ul
01 e s. i—
<— 3 3 IO U- ,
O O f~ cj ^
> s- -a ui o
c .e a* *•- co
•-* -p s-o ja
•*"•»
1 C
to o •
•P S. »-P
*•• O
-------
API-type separators. For gravity separation of oil in large holding
tanks, separators should be designed within the following limits: (a) hori-
zontal velocity of less than 3 fpm, (b) depth between 3-8 ft, and (c) depth-
to-width ratio of approximately 0.4. Oil is skimmed from the surface and
collected for reuse or disposal. Gravity separation is not effective for
emulsified oils that might be present in some retort waters (American
Petroleum Institute, 1969).
|
Sedimentation. This is a gravity process in which the solid phase
settles and, is withdrawn as a slurry. Clarification may be carried out in
large holding ponds, plate (lamella) settlers or hydrocycTones. Chemicals
(flocculants and coagulants) may be added to precipitate salts (softening) or
to aid settling of suspended solids (Humenick, 1977).
Flotation. This is a gravity process in which the solid phase rises to
the surface and is skimmed, off as a slurry. Air bubbles may be introduced
into the flotation vessels to assist separation (Humenick, 1977)1
Centrifugation. This is a modified gravity method to afford separation
or settling of fine, suspended matter and oils. The wastewater1is subjected
to a radial force greater than the gravity field by rapidly rotating it.
Suspended matter denser than water moves radially away from the center of
rotation, while the lighter matter moves toward the center. Concentrated
matter can be removed periodically or in a continuous manner. For continuous
operations, the sludge should be fluid to facilitate its removal. The
technology may not be applicable to highly viscous fluids. !
i
Coagulation - flpeculation. Fine particles suspended in [a fluid are
subjected to size enlargement by addition of chemicals (coagulants and
flocculants), then allowed to settle by gravity or under applied force.
Gentle agitation alone sometimes may afford the flocculation of the parti-
cles. The technology may also be applicable to liquid dispersions and liquid
particulates.
Chemical separation. Addition of chemicals to break emulsion may be
used in conjunction with filtration and is normally followed by gravity
separation. The type and dosage of chemicals required is determined by trial
(American Petroleum Institute, 1969). Chemicals may also be added to
precipitate salts or to increase crystal size.
Thickening. Slurries previously obtained from gravity, centrifugation,
and filtration: methods can be further concentrated, or thickened, by addition
of chemical agents or binders. The thickened slurry may then be'subjected to
the same methods for final disposition (Adams and Eckenfelder, 1974;
Humenick, 1977).
Solids filtration. The water stream is passed through a filter medium
which holds back the solid phase. Filters may be of the fabric type, as in
plate and frame, rotating drum (vacuum) and cartridge units, or granular, .as
in sand filters. Filtration is generally more expensive than sedimentation
but can remove smaller particles (Humenick, 1977).
237
-------
Filter coalescence. Gravity separation of oil from water is standard
industrial and refinery practice; however, the API-type separators are
inadequate for very small oil particles. One very important method for
removal of small oil droplets is coalescence (Water Purification Associates,
December 1975).
When a dispersion of micron-sized droplets of one liquid (oil) in
another (water) flows through an appropriate porous solid, coalescence of the
dispersed phase is induced and separation of the liquids results. The
dispersed phase can be allowed to accumulate without leaving the porous
medium, with periodic regeneration to remove accumulated oil.
Filter media are usually either the packed fibrous type .(e.g., fiber
glass, steel wool) or unconsolidated granular materials (e.g. ,• sand, gravel,
crushed coal). Because of their large specific surface and; high voids,
fibrous media are usually more efficient in removing droplets for a given bed
depth than are granular media. However, fibrous media are more susceptible
to blockage by suspended solids and are more difficult to regenerate, in
addition to being more costly than most granular media. :
Advantages of filter-coalescers include high separation efficiency for
dilute suspensions of very small droplets, potentially small space require-
ments, the possibility of continuous operation, and the potential for the
recovery of the dispersed phase. Disadvantages of this process are that
suspended solids can accumulate to require frequent medium regeneration or
replacement, and pumping costs can be substantial. As far as is known, the
system has not been evaluated on retort waters, and extensive pilot'plant
testing would be required to determine its feasibility on these waters.
Ultrafntratlon. Passage through a submicron-sized membrane filter
separates emulsified oil as well as suspended matter and large organic
molecules (MWt £ 1,000). The oil droplets are collected in the concentrate
and removed by gravity separation. This process is significantly more costly
than normal filtration (Water Purification Associates, December 1975).
Control Technologies Analyzed—
The streams that require removal of suspended matter, oils and greases
are: ..
• River Water (stream 140) .
* Foul Water (stream 29)
* Runoffs and Leachates (streams 12, 177, 178)
* Slowdowns and Concentrates (streams 168, 169, 175 or 176).
• • ' - . i
Colony has proposed obtaining the river water from the Colorado River.
While it does not contain any oils and greases, it does contain suspended
matter. Sedimentation by gravity settling and clarification with addition of
a!urn are the approaches proposed to reduce the suspended matter n'n the river
water.
238
-------
Table 5.2-2 presents the design features and cost data for clarifi-
cation, and Figure 5.2-2 shows a cost curve for the clarifier. This activity
could be considered as part of the process rather than pollution control.
TABLE 5.2-2. DESIGN AND COST OF RIVER WATER CLARIFICATION*
Item
River Water Flow Rate.
Flow Rate/Clarifier
Number of Clarifiers
Retention Time
Diameter
Alum Rate (30 ppm)
Fixed Capital Cost
Direct Annual Operating Cost
Maintenance @ 4%
Alum @ 12
-------
soi$ 'isoo 9Niivy3do
5
UJ
<
Of
LU
U.
O
s
-------
TABLE 5.2-3. DESIGN AND COST OF API OIL/WATER SEPARATOR FOR FOUL WATER
Item •'-,'..
Foul Water Flow Rate
No. of Channels (1 standby)
Channel Cross Sectional Area
Channel Depth
Channel Width
Channel Length
(channel is covered)
Fixed Capital Cost3
Direct Annual Operating Cost3
Maintenance @ 3%
Total Annual Control Cost0
Unit
gpm
103 Ib/hr
— '
ft2
ft
ft
ft
$103
$103
$103
Quantity
498
253
2
24
3 -;
8
65
140
3.4
31
3 '
The fixed capital cost and direct annual operating cost for the standby
channel are included. ;
Maintenance is based on the fixed capital cost less contingency.
See Section 6 for details on computation of the total annual control cost.
: ' • • ' ' i
Source: WPA estimates based on information from American Petroleum
Institute, 1969. ,
Service and fire water runoff, storm runoff, and leachate from shale
piles may contain oily materials. Again, an API-type oil/water separator
(without channel covers) was examined as the control. This will also allow
separation of suspended matter along with the water. The cost and design
data for this separator are given in Table 5.2-4, while a cost curve is
already included in Figure 5.2-3.
241
-------
a.
uj
cc
UJ
to
s
co
CM
20l$ 'ISOO IVJLldVO
UJ
u
0£
I
242
-------
TABLE 5.2-4. DESIGN AND COST OF API OIL/WATER SEPARATOR
FOR RUNOFFS AND LEACHATE
Item
Runoff Flow Rate
No. of Channels (1 standby)
Channel Cross Sectional Area
Channel Depth
Channel Width
Channel Length
Fixed Capital Costa
Direct Annual Operating Cost3
Maintenance @ 3%
Total Annual Control Costc
Unit
gpm
-
ft2
ft
ft
ft
$103
$103
$103
Quantity
126
. , 2
6
3 .
2
65 - •
27.4
0.7
8
:.....
The fixed capital cost and direct annual operating cost for the standby
channel are included. • .
Maintenance is based on the fixed capital cost less contingency.
See Section 6 for details on computation of the total annual control cost.
Source: WPA estimates based on information from American Petroleum
Institute, 1969.
The blowdowns, sludges, and concentrates from various processing units
will also contain suspended matter. These streams are collected in an
equalization pond for possible use in processed shale moisturizing. Since
gravity settlement affords separation of the suspended matter, the equaliza-
tion pond also might be viewed as a pollution control. Its design and cost
are presented in Table 5.2-5, and a cost curve is given in Figure 5.2-4.
5.2.2' Drssolved Gases and Volati1es
Dissolved gases include ammonia, carbon dioxide, and hydrogen sulfide,
while volatile materials are low molecular weight organics. Methods for
removing these substances from water are summarized in Figure 5.2-5. Steam
stripping is the most likely process to be used and has been successfully
demonstrated on a laboratory scale for some oil shale wastewaters (Hicks and
Liang, January 1981).
243
-------
TABLE 5.2-5. DESIGN AND COST OF EQUALIZATION POND
Item . Unit Quantity
Flow Rate into Pond gpm 2,600\
acre-ft/yr 3,770
Pond Area acre 2.7
Pond Depth ft 10•
Liner Material , __ Bentonite,
Fixed Capital Cost $1Q3 150;
Direct Annual Operating Cost $103
Maintenance @ 2%a 2.-4
Total Annual Control Cost5 $103 . 40 ,
Maintenance is based on the fixed capital cost less contingency.
See Section 6 for details on computation of the total annual control cost.
Source: WPA estimates.
Inventory of Control Technologies—
Table 5.2-6 presents an inventory of applicable control technologies,
along with their key features, for the dissolved volatiles. Basically, most
technologies involve stripping of the dissolved gases by either elevating the
temperature, applying vacuum, or displacement with carrier gases. More
specific removal can be accomplished by using an adsorbent selective for the
gas in question. :
>
Steam stripping. Steam stripping of sour waters (e.g., waters contain-
ing dissolved ammonia and hydrogen sulfide) and coke-oven liquors (e.g.,
waters containing dissolved ammonia and carbon dioxide) is standard practice
in the petroleum and steel industries. Stripping has also been used as part
of the "Phenosolvan" process on coal gasification process ! condensates
(American Petroleum Institute, March 1978; Beychok, 1967).
The dissolved gases are stripped from the solution by bubbling steam
through it, generally in packed or tray columns. The steam may be directly
sparged (live) or used indirectly in a reboiler, as in distillation columns.
The stripped gases, along with other volatile materials, are removed in a
relatively concentrated gas stream which may be treated for adsorption/
244
-------
,01$ ISOO 9NllVH3dO IVDNNV
o
a.
o
LU
t—
to
o
o
CM
tn
LU
ac
ts
Q3X!d
-------
DISSOLVED GASES
a VOLATILES
CONTROL
TECHNOLOGIES
STEAM
STRIPPING
VACUUM
DISTILLATION
INERT GAS
STRIPPING
ADSORPTION
SOURCE: WPA
FIGURE 5.3-5 DISSOLVED GASES AND VOLATILES CONTROL TECHNOLOGIES
246
-------
Ul
t—J
£
g
>
£3
i
VJ
Ul
• "O Ul
£5
Q.
CQ
u
XT 3 -M
01 CT -ui
Ot O) OJ
U. Q£ OS
O
C
f— Ot
(O «f—
> o
O *r>
1 <£
Q± Ul
' w
C
Ol "O
C 01
o >
II
1
a.
Ol
10
j-
Ol
a.
s1
I!
c u
a aj
O H-
= 2
0 0
Si-US*; . -.
•O 01
to o >»**- u
•M O O O
U C S.
•f- 13 01 > Q.
+J OJ -F- +*
Ul U) O -r- O)
3 3 •*- > -C
u ai
•o c
It 01
Q.T3 •
•i- O OJ
S. U 0)
t/5 3 ui
** *—
to »— 01 -i-
0) JO Q.-^
o •<- o •'5 > ^sl c
c in o > -MO
0 § !fl?,lJ£*- 0
o> to was s- s o o
Ul
4-1 C
-o wi"aiJi
u re •— to
. (8 U
Wl » - O
* 0) d*—* £.
3T (TJ CJ O >,
1
•o at
£= 3 -M
(TJ O 01 4*
»™ nj »— uJ
3 a> oi "S "e
•P > x: *— nj s
id '^ 4-* O Ol (O
S. +J > E. 01
01 f- JT ' o +^
toi O) ui C! U)
O 3 01 *<~
Q. 0 > • -0
<0 J= S C 01
C O) Of t-
•>• - C S UJ 01
«J -P» fO O >
(0 -0 0> . 'P- 0
a> -i- 4-> u c
S. > Wl Ol tO J=
*5 a.*o § o 's
Ol
e
Q.
a.
1
s
(O
•01
V?
UJ
c s
01 r— 01
1* Q.W .
•»-- u» oi
3 4J (O r—
O* Ul O)^ .
, 01 o c c to
>j-a a> a. ia
O) O > *r- >
01 -M 4->
C T» Ul >)
ai .+»,£?
Ul 01 0) '»-
j= +j a. s- -a
o> c e a* to
•*• ai o -c o»
Z £ U S t.
V)
01
tn
to
Ol
•a
Ol
to
Ol
o
(0
Wl
+j
(0
Ol
Q.
I
S u»
O Ul
^- 01
01 1.
£. a.
3
U> 01
tn c
O) *r-
• S. a.
a. a.
— J UJ
e
o
to
§£
3 •)->
U Ul
tO "f"
> a
>> i
C G
at o
5 c
S O
S <— ui
T5 . O1
Ol •*£-•*->
UJ 01 O ui
3 b. 4> fO
3 S
>»xJ 01
<— s- ^ o
(13 0) (O -f-
O 0) 3 !-
Z +J UJ *J
(0 Ol
tn
•O (O
Ol Ol
•It
k. ai
4-» C
to •»-
a!
Ul
•^
01
o
Ul
o
10
UJ
3 Ol 0)
^ -C U
4-> (B
•> O f"™
S -""
v oi id
4-» O> O*
UJ O
1. -M
S J-» S.
10 «p— ai
a, c c
4*> "
ui cO ^ (O
(0 id oi
O) C •— u>
JUJ > <*-
3 (d O
Ul Ol
35
-a
s- •"
ss
»— t tn
(S
' Ul
O
O) V)
QS ro
0) C •
r— O Ul
JS U C
(O O
4J g; ir*
5 -r- (0
Ul ^C t.
4J
4J S. C
O O Ol
Z l^- U
f-» Ul
0 0 •
01 oi >~*
i, *r* <^
o **-
JZ-r- ui
O)**- ui
•r- <+- O
X Ol Q.
01 ui
*— O
* ,
S*^ o 2
p
ex
o
Ul
3
-------
recovery of a specific substance or incinerated. Carbon dioxide is readily
stripped at efficiencies of +99%; ammonia strips less easily, and pH eleva-
tion may be required in some cases for 99% removal. Hydrogen sulfide does
not strip as easily as carbon dioxide but can generally be removed down to
the 10-20 ppm range. Costs are for equipment and steam and are proportional
to the volume of water to be treated. '
Steam requirements range from approximately 10 to 15 Ibs steam per
100 Ibs water treated. For a given separation, a greater column height is
required for a lower steam rate. The selection of steam rate and column
height is based on energy and equipment costs.
The stripped gases may be incinerated or treated further to recover
ammonia and sulfur. Ammonia may be recovered as anhydrous ammonia, aqua
(20-30%) ammonia or ammonium sulfate. In cases where the sulfate is derived
from flue gas desulfurization, the sulfate route may be viable depending, in
part, on the marketability of ammonium sulfate and on the costs of alterna-
tive flue gas desulfurization processes. Because oil shale plants generally
will have ammonia available as a by-product, S02 scrubbing with NH3 may be
attractive when the technology is sufficiently developed :and tested.
Recovery of anhydrous ammonia involves considerable capital and energy
(steam) requirements, but these are partially offset with by-product ammonia
sales. The stability of the ammonia market must be considered when selecting
a recovery process. ,
Vacuum distillation, Distillation at reduced pressure has many
industrial applications, but these primarily involve distillation or
fractionation of compounds with high boiling points or low thermal stability.
The method may be applicable to stripping of gases and volatile compounds,
but the energy requirements are high relative to those for steam:or inert gas
stripping.
low
Inert gas stripping. This method is applicable to dilute, or .,..
strength, wastewaters for which steam stripping may not be practical. The
operating principle is similar to that for steam stripping, except/air,
nitrogen, carbon dioxide, or other inert gases may be used. Its application
to high strength liquids is generally not practical because large column
heights and gas compression costs are required. ,
Adsorption. Dissolved gases and volatile components may be adsorbed on
specific surface-active materials by passing wastewaters through ;a bed of the
adsorbent. The gases may then be desorbed thermally, and the regenerated
adsorbent is recycled. This method is generally used in trace removal
applications.
Control Technologies Analyzed—
The streams that require removal of dissolved gases and volatiles are:
* Foul Waters (streams 29, 30, 99)
• Sour Water (streams 110, 124).
248
-------
The foul waters are previously freed from the separated oil and emulsion
in the oil/water separator, but some polar organics (e.g., phenols, fatty
acids) remain dissolved. A portion of the dissolved organics ,can be steam
stripped along with other dissolved gases. The foul waters also contain
free ammonia, hydrogen sulfide and carbon dioxide. Steam stripping removes
these dissolved gases and most of the volatile organic matter. A further
control of the released ammonia is also desirable and this may be accom-
plished with an ammonia recovery unit. Design parameters and cost informa-
tion for steam stripping are given in Table 5.2-7, and a cost curve based on
this specific design is presented in Figure 5.2-6. The description and
material balance for the stripper are presented in Sections 3.3..3 and 4.2.7,
respectively.
Steam stripping and ammonia recovery were examined as controls for the
sour waters, the design specifications for the ammonia recovery unit for all
case studies are given in Table 5.2-8, while the costs are .presented in
Table 5.2-9. Figure 5.2-7 presents a cost curve for the ammonia recovery
unit specifically designed for treating the TOSCO II sour waters. The
process description for the unit is given in Section 3.3.11 arid a material
balance for the process is included in Section 4.2.7.
5.2.3 Dissolved Inorganics
Dissolved inorganics are usually not a problem unless the compounds are
judged to be hazardous (e.g., trace metals) or when fouling of equipment
(e.g., boilers) occurs because of the high salt content of the!waters being
used. Natural waters and waters that come into contact with the solids may
need to be treated if they are intended for critical uses in the plant.
Processed shale moisturizing, on the other hand, may not require control of
dissolved inorganics. In fact, waters with high salt content can be used for
this purpose, thereby avoiding the need for. other controls.! Since gas
condensates do not contain significant amounts of dissolved inorganics, a
treatment may not be necessary.
Inventory of Control Technologies—
Methods for removal of dissolved inorganics are shown in Figure 5.2-8,
while some of the key features of the technologies are presented in
Table 5.2-10. The operating principles for some of the methods ;shown in the
figure are detailed below.
Precipitation. Chemicals may be added to precipitate salts, e.g., lime .
addition for carbonate (hardness) removal. Processed shale is also believed
to behave like a softener for inorganic carbon reduction (Humenick, 1977).
The process is simple, but it will usually require the use of other methods
(e.g., gravity separation, centrifugation, filtration) to remove the precipi-
tate. ...
Ion exchange. Cations and anions in solution are replaced With hydrogen
and hydroxyl ions on exchange resins capable of producing a water virtually
free of common salts. The resins are regenerated with relatively strong acid
and alkali solutions, and the regenerant wastes must be controlled. Costs go
, 249
-------
TABLE 5.2-7. DESIGN AND COST OF FOUL WATER STRIPPER
Design Parameter
Foul Water Feed Rate
Steam Rate
Cooling Water Circulated
Stripping Column
Number
Diameter
Height
Material
Reboi 1 er
Number
Surface area
Material
Partial Condenser
IN umber
Surface area
Material
Feed Heat Exchanger
Number
Surface area (each)
Material
Fixed Capital Cost
Stripping column
Heat exchangers
TOTAL
Direct Annual Operating Cost
Maintenance @ 4%a
Labor, 12 hr/day @ $30/hr
Steam @ $3/MMBtu
Cooling water @ 3
-------
S0l $ '1SOO 9NllVH3dO 1VDNNV 133am
o
o
vo
a.
a.
LU
o:
LU
01
8
in
LU
Of.
ts
s
o
o
o
o
CO
eOl$ 'ISOO iVUdVO Q3XU
LU
O
251
-------
TABLE 5.2-8. DESIGN OF AMMONIA RECOVERY SYSTEM*
Design Parameter
Sour Water Feed Rate
Ammonia Rate
Steam Rate
Cooling Water Circulated
Electricity
Chemicals
H3P04
NaOH
Steam Stripping Column
Number
Diameter
Height
Material
•Reboilers on Steam Stripping Column
Number
Surface area
Material
Phosam Absorber
Number
Diameter
Height
Material
Reboiler on Phosam Absorber
Number
Surface area
Material
Cooler on Phosam Absorber
Number
Surface area
Material
Phosam Stripper
Number
Diameter
Height
Material
Unit
gpm
Ib/hr
103 ib/hr
gpm
kW
Ib/hr
Ib/hr
—
ft
ft
--
—
ft2
-—
—
ft
ft
„„ .
„=
ft2
«*«=»
• —
ft2
-—
--
ft
ft
—
Quantity
510
11 , 208
156
6,900
300
19
120
1
6.0 .
95
CS/SS
1
1,400
CS/SS
1
5
50
SS
• .
1
4,175
CS/SS
1
5,640 .
CS/SS
1 .
8
60
SS
(Continued)
252
-------
TABLE 5.2-8 (cont.)
Design Parameter
Unit
Quantity
Condenser on Phosam Stripper
Number
Surface area (each)
Material
Ammonia Fractionator
Number
Diameter
Height
Material '•'..'
Fractionator Feed Tank
Number
Diameter
Height
Capacity
Material
Reboiler on Fractionator
Number
Surface area
Material
Condenser on Fractionator
Number
Surface area
Material
Flash Drum
Number
Diameter
Height
Capacity
Material
Lean Solution Cooler
Number
Surface area (each)
Material
Solution Exchanger
Number
Surface area
. Material
_=
ft2
=—
__
ft
ft . ;
' —
.
ft
ft
gal
-—
—
ft2
-—
—
ft*
-—
-
ft
ft
gal
„_
ft2-
— — , .
--
ft2
~
2
3,380
SS
i
1
3.8
64
SS
1
7
26
7,250
SS;
i
1,240
CS/SS
1
3,835
CS/SS
1
4
9;>-
820;
S5
2
4,625
cs/ss;
; •• • • -.-- . .
1
1,810
SS
* This table is based on the Phosam-W process, which is only one example of
many available processes for the recovery of ammonia.
Source:. WPA estimates based on information provided by U.S.S. Engineers and
Consultants, Inc., April 1978.
253
-------
TABLE 5.2-9. COST OF AMMONIA RECOVERY
Item Unit
Fixed Capital Cost $103
Towers
Heat exchangers
Drums, etc.
TOTAL
Direct Annual Operating Cost $103
K
Maintenance @ 4%
Labor, 24 hr/day @ $30/hr
Steam @ $3/MMBtu
Cooling water @ 3$/m3 circulated
Electricity @ 3$/kW-hr
Chemicals
NaOH (475 tons/yr @ $350/ton)
H3P04 (75 tons/yr @ $474'/ton)
TOTAL
Credit for Ammonia Sales @ $110/ton $103/yr
Credit for Low Pressure Steam Return $3/MMBtu
Total Annual Control Costc $103
Quantities
Example Ia 'Example IIa
1,945 2,035
2,614 2,729
100 105
4,659 '. 4,869
152 158
237 i 237
2,653 2,834
345 . 369
71 76
166 • 180
35 : 38
3,659 ; 3,892
4,878 ! 5,203
183 229
(122)d --*
In Example I, the foul water stripper overheads are not fed to the ammonia
recovery unit. Example II reflects recovery of additional ammonia from the
foul water stripper overhead.
Maintenance is based on the fixed capital cost less contingency.
c See Section 6 for details on computation of the total annual control cost.
Value in parentheses ( ) indicates that the annual by-product credit is
higher than the total annual control cost.
Q
Example .II is not part of the case studies; therefore, the total annual
control cost was not determined for it.
Source: WPA estimates based on information provided by U.S.S. Engineers and
Consultants, Inc., April 1978.
254
-------
£0i$ 'iSOO 9NUVH3dO 1VITNNV 103810
t/5
8
«M
m
O
i— i
lu,
£0l $ '1503 IVildVO C33Xld
LU
O
255
-------
DISSOLVED INORGANICS
CONTROL TECHNOLOGIES
SOURCE: WPA
CHEMICAL
PRECIPITATION
ION EXCHANGE
MEMBRANE
PROCESSES
EVAPORATION
FREEZING
SPECIFIC
ADSORPTION
REVERSE
' OSMOSIS (RO)
L- ELECTRODIALYSIS(ED)
i—THERMAL
VAPOR
COMPRESSION
FIGURE 5.2-8 DISSOLVED INORGANICS CONTROL TECHNOLOGIES
256
-------
8
M
§
O
3
O
a
01
£
3
3
§
«j
s
•S
z
s
o
V)
UJ
1
5-
£
S
I
UJ
ca
Comments
By-products
and Wastes
-•S
Ul Ul
*» C
£s '-M
41 U
i. •*-
•O 3 4J
o> cr 01
(U Q) (U
1
•3.1
> u
iC
Ol <+-
OS UJ
Ul
c
o >
CJCC
at
A
£.
a.
O)
c
.p
s
ai
s-
01
O
C u
0 HI
O 1—
Generally followed by
filtration and/or
activated carbon
adsorption.
to ui
•*-» .C r—
C *> «
O .1- 4J
U 2 (U
oil! >>
?^3
f— c a>
(/»-•*- j:
•a
i." £
Is ¥
'o rtJ 2
O <0
- U) ^
-r-"c ra*
C U)
, O •+•>
C
- OJ Of
0) C 3
^s ~a -^
(U C -P
tas
5-SS
^
(0 .
O) >,
.
« • c
E "S*"
ai
Use of agents to promoti
the precipitation .of
inorganic solids from
wastewaters.
c
o
' 4-*
to
U 'S.
-C £
CJ O.
Most effective as a
polishing process.
Clearly applicable to
boiler feedwater treat-
ment needs; of limited
Spent
regenerants
and resins.
Ul 4J
*> c
C 4)
4) O ui
c m c:
01 CL u»
C
(Q
-C
U
X
U4
C
o
M
use in treating process
wastewaters containing
high concentrations of
organics or dissolved
solids.
RO and ED have been used
cogunercially for desali-
nation. Concentrate
stream aay be 10-30% of
input stream.
Ul
Concentrate,
spent membran
£
Q.
C **
O C
ca +5 c 'o
s- u> to s-
r- •r-s's C
-F- XJ O O
U- « *4- U
_
> T3
O QJ
8-3
s. o
Ul
a^ ui .
S -5 -13
0 M- '(O
<7> O W
£
(0
U>
T3
U) Ul
cn-fcj en £
C (0 C
•r- C
0 ^^0
-t^ r— (/i
O i. S_
Q. O) Q.
m ..c e
UJs^O
has been successfully
tested on retort waters.
1
si
43
•o
c
>
Ol
s_
Q.
Not yet demonstrated
commercially.
Concentrate
stream.
0)
-^
W)
Ul
o
a.
¥
o
(71 -
U)
'in
Ul
"O -O) .
<1> C Ul
"o ~s'ei
tn i— to
y. " g>
fc
Cooling with formation o
ice which is separated
from remaining brine.
jf
ISJ
4>
4»
£.
U_
Useful as a polishing
process.
4)
Q
03
u>
0
Ul !
zi !
4) 4->
CL 01
2 UT* '
_c|
cn '
O 41
1
'£ ui
So
I— 4->
1 1 1
&~ lO
O S, ;
CO +J
C.
o o
•»- Ul
<*- £.
U J=
41 4J
, CL O
Ul
•I— U»
*> 4t
0 O
•S "e
c
u-2
!£ S*
0 0
41 ui
01
-------
up with increasing concentration of salts in the water. Ion exchange is
normally used only where a very clean water is required from a relatively
clean or mildly brackish supply. The brganics present are not removed and
may foul the exchange resins (Calmon and Gold, 1979). :
Reverse osmosis (RO). Sometimes called "hyperfiltration;" RO is a
process for recovering, relatively pure water from solutions. Water is passed
through a hyperfiHer, or semipermeable membrane, which rejects dissolved
materials. As in normal filtration, the driving force isi hydrostatic
pressure, but in this case, the pressure has to be greater than the osmotic
pressure of the solution. Osmotic pressures are related to the total molar
concentration of the solution and its temperature (Hicks and Liang,
January 1981).
The water is passed under pressure (greater than 200 psi) through a
membrane which is impermeable to most inorganic salts and many organics.
These "rejected" substances remain in a concentrate stream which may be
.10-20% of the feedwater volume. The treated water or permeate will generally
contain less than 10%, and often less than 1%, of the rejected substances.
Costs scale primarily with the volume of water to be treated but are also
dependent on concentration. At very high solute concentrations (e.g.,
seawater), costs increase rapidly due to the high applied pressures that are
required. The flux of water through the membrane, i.e., the permeate recovery
rate, increases linearly with the pressure by which the applied pressure
exceeds the osmotic pressure. Fluxes of 10 gal/ft2/day have been measured
for retort water at an applied pressure of 600 psi. Typical applied
pressures for brackish waters range from 200 to 600 psi and greater.
_ • . • _ ...... ... . j
Membranes consist essentially of a thin skin (0.1 to 0.25 urn) of active
chemical (cellulose acetate, polyamide) on a porous substructure, which may
then be housed in a spiral-wound module for commercial application. Other
geometries are also available. Rejection of strong electrolytes is normally
in excess of 90% and can exceed 99 percent. Nearly complete rejection is
obtained from most species with molecular weights greater than about 150.
However, low molecular weight nonelectrolytes (e.g., small organic molecules
like urea, and weak acids such as boric acid) are poorly rejected. Rejec-
tions of these substances can sometimes be improved by adjusting the solution
pH to a value where the compound dissociates (e.g., boron is rejected above
PH == io). .-.;-.
\ • • •
Some advantages of RO treatment are the low labor and space requirements
and the high rejection rates obtained for a wide range of dissolved contami-
nants. Of particular relevance to oil shale retort water is that both
organic and inorganic compounds can be simultaneously removed under favorable
pH conditions and that such a system can accommodate changing water flow
rates. A serious disadvantage of the process is that the membranes are
susceptible to blockage by deposition of solids. This so-called fouling .
results from solids present in the feed solution or from precipitation of
solids as the concentration in the brine exceeds the solubility limit; it may
even result from biological activity on the membrane surface. :
258
-------
Fouling rates may be reduced by proper pretreatment and by reducing the
concentration increase in the brine. Reverse osmosis does not destroy the
pollutants, it merely concentrates them into a smaller liquid stream.
Reducing the concentration increase implies reducing the product recovery and
increasing the amount of brine for disposal. Fouling can be further
controlled by periodic washing, although there is generally a certain amount
of irreversible fouling that determines membrane life and operating costs.
Costs scale proportionately with the volume of product water recovered,
but they are also dependent on the degree of recovery and membrane fouling
characteristics. As the concentration of pollutants in wastewater increases,
so does the osmotic pressure; hence, higher applied pressures are required to
maintain the desired permeate flux. Energy costs, however, are normally
small relative to membrane costs. !
Electrodialysis (ED). Electrodialysis is the use of an electromotive
force to transport ionized materials in a solution through a diaphragm, or
membrane. The process can be made selective by using ion-specific membranes
which allow passage of only certain ions. A common application of electro-
dialysis is in the desalting of brackish waters containing 1,000-5,000 ppm of
salts. A removal efficiency of 90-99% is usually achievable.
Thermal evaporation. This approach includes .processes in which heat is
applied to vaporize water, leaving a concentrated solution or slurry for
disposal. The high energy required for evaporation is recovered in most
processes by condensing the water vapor and, as a result, producing a stream
of relatively pure water. Volatile contaminants, if present, may require
removal in an upstream stripping process in cases where a clean product water
is necessary. Multiple effect boiling (MEB) and multistage flash (MSF) are
two procedures commonly used for evaporation (Water Purification Associates,
December 1975).
' Disadvantages of thermal processes are that volatile substances are not
controlled, and (energy) costs are generally higher than for processes not
involving a phase change. Problems related to scaling of h£at transfer
surfaces and corrosion are also encountered. These problems may be accentu-
ated with waters containing high organic loadings, such as oil shale waste-
water. Thermal processes may find application if there is a need for dirty
steam, as occurs in many in situ processes.
Vapor compression evaporation. This is a method for evaporating water
by the use of mechanical energy. Thermal energy required for evaporation is
obtained by mechanical compression of the vapor instead of by heating. The
wastewater is boiled in an evaporator to produce a vapor which is compressed
in order to raise its temperature, and then it is passed through :the tubes in
the, evaporator where the necessary heat exchange between the vapor and
wastewater takes place. The vapor cools and condenses upon heat exchange and
a relatively pure water is produced. :
The advantage of vapor compression is that the heat required for vapor
formation is recirculated so that the amount that must be dissipated is much
less than the latent heat of vaporization. This approach; results in
259
-------
relatively low energy requirements and essentially negligible cooling water
requirements. The penalties are the high capital costs associated with the
compressor, which must handle the large volumes of vapor, and increased
maintenance costs. Other disadvantages of vapor compression evaporation are
'similar to those of the thermal processes.
The energy required for the single effect vapor compression units is
about 70-90 kW-hr per thousand gallons of product water. Some single effect
vapor compression units (RCC evaporator) can recover up to 98% of the waste-
water containing up to 11,000 mg/1 total dissolved solids. :
. Freezing. The water is reduced in temperature to produce a solid (ice)
phase and a concentrated brine. The ice is washed free of salts and then
melted to produce a virtually pure water. Both inorganics and organics are
removed in the brine stream. Since the costs scale with the volume of water
to be treated, freezing would normally be applied to relatively concentrated
low volume wastes. While this process is theoretically more efficient than
evaporation, it has yet to be applied commercially. It is included in this
inventory as it may be useful for controlling retort waters, provided
operating problems can be resolved in the future (Barduhn, September 1967;
Water Purification Associates, December 1975).
Specific adsorption. The processes in this category are similar to the
ion exchange processes, except that the affinity between the sorbent
materials and the solutes being removed is of a physical nature. The
sorbents may be natural or synthetic and usually have pores, or lattice
vacancies, of uniform size and dimensions which are specific for the solutes..
The processes are not applicable to high strength wastewaters and are
generally used for trace removal applications.
Control Techno!ogles Analyzed—
The following streams may require control of dissolved inorganics:
• Boiler Feedwater (streams 153, 154, 155, 156, 157) '
» Cooling Water (streams 141, 142, 143, 144, 145, 146).
Softening was examined as the most economical treatment of the river
water makeup to prevent seal ing'in the boilers. In this process, calcium and
magnesium ions are replaced by sodium ions using a zeolite ion exchange
resin. Total dissolved solids and silica are not removed by softening, and a
relatively large boiler blowdown is required to maintain acceptable concen~
tration levels in the boilers. The boiler blowdown is used for processed
shale moistening. The blowdown does represent an energy loss from the boiler
system, and some heat recovery from this stream might prove cost effective.
The zeolite softener is regenerated with a saline solution prepared from salt
and clarified river water. The waste regenerant, containing mainly calcium
chloride, is disposed of on the processed shale after equalization with other
blowdowns. Table 5.2-11 gives the basis for design and costs of boiler
feedwater treatment, while a cost curve for the zeolite system ITS presented
260
-------
in Figure 5.2-9. The boiler feedwater treatment could be considered as part
of the process rather than pollution control.
TABLE 5.2-11. DESIGN AND COST.OF BOILER FEEDWATER TREATMENT3
Item Unit',.. .Quantity
Boiler Slowdown (20% of softened gpm 280
river water makeup)
Steam Consumption and Losses gpm 1»120
TOTAL MAKEUP (clarified river water) gpm ; 1,400
Fixed Capital Cost (includes one spare train) $103
Resin: 940 ft3 @ $50/ft3 .47
Installed equipment 361
Contingency and contractor fee 83
TOTAL 491
Direct Annual Operating Cost $103
Maintenance @ 4%b ; 14'
Labor, 2 hr/regeneration @ $30/hr ' 66
Chemicals
Resin replacement @ 3% per year 2
Salt @ $45/ton . : 290
TOTAL 372
Total Annual Control Costc $103 474
* This technology could be considered as part of the process rather than
pollution control.
Maintenance is based on the fixed capital cost less contingency.
See Section 6 for details on computation of the total annual control cost.
Source: WPA estimates based on information from Peters and Timmerhaus, 1980.
Clarified river water is used as cooling tower makeup. As a treatment,
some sulfuric acid is added to convert calcium carbonate to the more soluble
calcium sulfate. The cooling tower is operated at two cycles of concentra-
tion, which means that the concentration of dissolved species in the blowdown
is twice that in the makeup. Since this concentration is not excessive, the
I
261
-------
£0l$ '1SOD
IVIINNV iOHMIQ-
o
o
in
O
O
\
o
o
o
o
O
O
\o
o
o
o
o
ut
OS
s
O
o
o
LU
§ <
§ at
o
o
o
Of
LU
i
LU
U_
O
CO
o
o
CPk
CM
LU
on
o
CM
O
O
'1SOO IVlldVO d3X!d
ca
o
to
262
-------
cooling, tower (slowdown may be used for processed shale moisturizing.
Table 5.2-12 contains design and cost information for the cooling tower
makeup treatment, and a cost curve for the treatment is shown in
Figure 5.2-10. This technology could be considered as part of the process
rather than pollution control.
TABLE 5.2-12. DESIGN AND COST OF COOLING WATER TREATMENT3
Item
Evaporation and Drift Losses
Slowdown
TOTAL MAKEUP (clarified river water)
Cycles of Concentration
Su'Jfuric Acid Addition
Unit
gpm
gpm
gpm
--
mg/1 (ppm)
ton/yr
Case
A, B
1,530
1,530
3,060
2
71
428
Studies
C
1,646
1,646
3,292
2
'71
461
Direct Annual Operating Cost $103
Sulfuric acid @ $65/ton 28 30
Total Annual Control Cost 29 31
.n^™~!T'~--.-.-"-"i-"'•••'-'-.,_ -_ ~""~^~:.-~.". _r_ll_ll[MJ.'",T""J".^V.'L'J"L.'. - ' '1.1..Z"""~. ".__"'"C"V~; ':.'' .' T~rrr""T'-:i- "". ' ' _•__; . --..I. I. I....
/•'.". ' ' '< ' """"
This technology could be considered as part of the process rather than
pollution control. ;
See Section 6 for details on computation of the total annual control cost.
Source; WPA estimates based on information from Peters and Timmerhaus, 1980.
Other Control Technologies Analyzed—
One additional dissolved inorganics control technology—a solar evapora-
tion pond—was evaluated as a post-treatment for the process waters. A solar
pond is simply a lined pond with enough surface area to provide an evapora-
tion rate that is higher than the rate of inflow. The precipitated sludge
can be removed periodically and disposed of in a proper manner. This
technology has not been proposed by Colony; however, it was analyzed as a
viable option in the event that the process waters are reused 'in the plant
and the resulting wastes are disposed of separately from the processed shale.
263
-------
UJ
Q£
O
o
o
CO
o
o
esi
ac
£oi$ 'isoo
UJ
o
a:
264
-------
For example, the foul water after steam stripping can be concentrated by
evaporation, whereby most of the water and volatile components would be
removed. The foul water concentrate can then be subjected to chemical
oxidation to destroy nonvolatile organics. At this point, only nonvolatile
inorganics should remain in the oxidized sludge. The sludge can then be
placed in a solar evaporation pond for further concentration of the
inorganics. If the treated foul water is used as makeup to the boilers or
cooling tower, the blowdowns from these operations can also be placed in the
solar pond. A flow scheme depicting the above treatment and reuse options,
when applied specifically to the TOSCO II process waters, is 'presented in
Figure 5.2-11, the design and cost data are given in Table 5.2-13, and a cost
curve for the pond is presented in Figure 5.2-12.
TABLE 5.2-13. DESIGN AND COST OF SOLAR EVAPORATION POND
Item Unit Quantity
Flow Rate, to Pond gpm 214
acre-ft/yr . 311
Evaporation Rate in/yr 15
Pond Area acres 300
Liner (chlorosulfonated polyethylene) 103 ft2 13,000
Fixed Capital Cost $103 16,600
Direct Annual Operating Cost $1Q3
Maintenance @ 2%* 270
* Maintenance is based on the fixed capital cost less contingency.
Source: WPA estimates.
5..2.4 Dissolved Organics
Removal of volatile organics by stripping may be sufficient for reuse of
process waters in processed shale moisturizing; however, nonvolatile organic
components are not removable by stripping. Therefore, for higher quality
uses, further treatment may be necessary. Some of the available approaches
are discussed below.
Inventory of Control Technologies—
The technologies available for dissolved organics control are shown in
Figure 5,2-13 and are described in Table 5.2-14.
-*,
265
-------
FLOWS IN 6PM
FOUL WATER
SOUR WATER
LOSSES
[3D •
498
FOUL WATER
STRIPPER
510
AMMONIA
RECOVERY
468
19
LOSSES
,487 1,
VAPOR
COMPRESSION
EVAPORATION
441
i
46
CONCENTRATE
WET
AIR
OXIDATION
TO HYDROTREATERS '
485 *
H _. rn 7IH CUD nr^nurn
LOSSES
J2I4
45 SOLAR
SLUDGE POND
BOILER ' ' . .
FEEDWATER
J848
CARBON
ADSORPTION
441
CLEAN WATER
STEAM
GENERATORS
i
169'
SLOWDOWN
' 1 120
SOURCE: WPA
STEAM
FIGURE 5.2-11 FLOW SCHEME FOR SOLAR EVAPORATION TREATMENT
266
-------
'ISOO 9NllV«3dO 1VONNV J.038IG
o
•z.
o
a.
ce
3
o
u.
o
to
s
UJ
Of
=3
a
i*^
u.
90l$ '1SOO IVildVO 03XIJ
o
0£
O
to
267
-------
DISSOLVED ORGANICS
CONTROL TECHNOLOGIES
SOURCE' WPA
BIOLOGICAL
WET AIR
OXIDATION
CHEMICAL
OXIDATION
THERMAL
OXIDATION
MEMBRANE
PROCESSES
ADSORPTION
FREEZING
SOLVENT
EXTRACTION
EVAPORATION
DISPOSAL AND
CONTAINMENT
r REVERSE OSMOSIS (RO)
•ULTRAFILTRATION(UF)
E CARBON,
RESIN !
PROCESSED SHALE
STRIPPING
COOLING TOWER
SOLAR
FIGURE 5.2-13 DISSOLVED ORGANICS CONTROL TECHNOLOGIES
268
-------
l/> ,
u
z:
o
ca
tU
>
_j
S?
l/l
a
a:
o
u*
UJ
3
3
5
—i
o
05
ci
l/)
UJ
C£
1
UI
Ua
'i!
S
«vl
1
U)
+J
§
3'
+J U>
"O in
i.^
mi.
UI' U)
4J =
c o
o *f—
£ *J
2O
.;:
•r- S-
•a 3 *j
a» cr ui
O» ^
u
•3!
> £
€ C
at v.
Q£ UJ
Ul
c
o» -o
c a>
o >
o 3
CJQ£
0)
*Q.
1
a.
O)
c
**j
(0
S.
1
§
o
o o
t. c
•u x:
o o>
o f—
t»
UJ 01 v» O)
01 O»< £ 01
•«- (TJ *3 ^
+J r— « OJ O* CO
W C 0) r—
0 O r- •£ S. * Ul
41 3 -o « a>
•a o* s >
•r* a> » u» nj •*•» ^—
C (13 *f- ^ (TJ U
O TJ £ O) J= C
04 .Q
S 2
. at
- tj nj
at *^- c •
O.Q to •
r-« 0} -r- 0)
« flj U
a 4* o
•i- c x i-
co — cj a.
0) t. •"
-C O 0) Lp
"O *J 4J J3 O >K
O) C 01 S. S_ .— (0 .
aiatms-o OT-+JOI ros-o
*— 3 3 3 C. Crt fc
T> 2 m S..^ 1"*e"s^s'c etuaio*
i— CE*O nj CTC.CUJ ^"O UICL-P
£• ' CJ
**- o <;
o 't- ui a.
£_
"^ "m 4J >»J3 o
> U CO O
0 -r- 3 C TJ C
e a. co o) o
ai >,-u «f- u T-
s- +J a- u c 4J
O O 0) •*• C TJ
LD t— — UJ O» (TJ
a
o
CJ
S . ' "
— - ,
1 . • -
*o
5 o»
u
o t=
O •*•> 0)
CJ t/1
g.*»
u ai m
3 JS •>-
o o> a>
CJ &. C 4->
" O • fc **" ' (8
+* O *-* 43 - •
O
O U jQ O)
•^ •»- O T3
*J J3 S- C
T) o at o>
"D S- «J Q.
X (O ft) 3 -
*«
0
en
0
"o
5 • .
« « «
U 3 »—
r"~ i_ *r~
§ g-.?5
3 ^ ^ S
Proini s 1 ng
proven in
tion. Fa
construct
i
c
0
U u)
in Ol t-
+•» C - !-
01 ffl O >»
_ > *» CJ JS
c"
o> .
Q) CJ
O t- C
O *J +J
i, X C
H- 05 O •»-
*^T3
O w* S.
O 0) 0)
lpn, (^ > ^
Of 0) N
S- +* -r- -O
fO &. 0>
4J 3 3 4->
O 0> u) (O
Q S 0.4)
C .
O
+J
(8
•o
I
s-
+J
dt
3
CT
•£
£1
>g
<2
u>
z:
s_
(0
c
o
+J
c
o
O)
i
S!
u
Q.
tft
J
0>
1/1
i-
+J
o
s-
!&
'Sfe
T3
•(->
VI (1)
3 ^.
"S U^
Chlorine-t
oxidants i
problems v
wastewatel
1
m
Ul £.
0) 0)
ui +J C W
0) •••> 3
> § £ Q.
c
X
o
r— C
m a. o
> 3
§^s§-
8
CJ
o
I* a» *x m
OS 3 0.0
c
o
^
m
•o
I
>
uj -a o'-.-'i-
« 0) C 0) •*•> Ul
s: u « at
^ o) x >, jj- a.
J-t W 2C S'LU «
0)
Ul
01
IT
^|1| g
i S S ^ 5
"S "c -a S £
ai c *" o-4J nj
a> o o ai to >
U>
r— Ul
UJ i-l Q.-O
s
nj
'x-2
® S
< o
52?
-w *3
u> _s
1 »
s- at
Ul -P -4-»
u u) m
•r- S-
C S- 0
030)
G
o
^rj
.-§
I
1
0)
3 |
C (A
iU !
s § ' •
B =
O)*—
§i
— i 4- i
4->
C
as ui u)
c'S S
0) (0 t-
cS ui 3
c ;
* 41
•r- UJ Ul
1o •3s'« c :
•^ X 0) O
v»
M— O) -M
O r— C
in ui u
0) "A
u s- M ja ^-*
e - S § -3
oij*C«*' *^" Ei>
« 3 o> c *b
.i. j. 3
T3 £ aj <*—
3 1.
S. >» 3 '
nj s. nj o)
^